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In this work, La0.8Sr0.2MnO3 (LSMO) nanopowders are synthesized using two different methods: Pechini (LSMO-PC) and auto-combustion (LSMO-AC). Nanoparticle sizes, structural, magnetic, and magnetocaloric properties were determined and compared. The X-ray diffraction confirms the coexistence of two phases; rhombohedral symmetry with space group R-3c and orthorhombic symmetry with space group Pbnm, with the rhombohedral phase dominating. The scanning electron microscope images show that LSMO-PC has larger nanoparticle sizes (~495 nm) than LSMO-AC (~195 nm). The samples exhibit ferromagnetic properties with distinct hysteresis loops and Curie temperatures 340 K and 290 K for LSMO-PC and LSMO-AC respectively. The variation of the magnetic entropy was measured indirectly using the Maxwell approach with increasing magnetic field. For LSMO-PC it reaches a maximum -dSM=1.69 J/kg.K at 340 K and dH= 5 T. The associated adiabatic temperature change dTM is 1.04 K. While LSMO-PC demonstrates superior magnetic and magnetocaloric properties, LSMO-AC displays significant magnetocaloric thermal stability. The obtained values make LSMO-PC and LSMO-AC promising candidates for eco-friendly room-temperature magnetocaloric applications.

A series of (1-x)[(2BaO-0,5Na2O)-1P2O5] -xNb2O5 (BNPN, x=0,41, 0,43, 0,45, 0,48) glass-ceramics based on phosphate glasses have been prepared via a controlled-crystallization route. The structure, dielectric properties, interfacial polarization, and energy storage properties were systematically investigated. The x-ray diffraction results showed the simultaneous presence of Ba2NaNb5O15 tungsten bronze structure (TTB) and the NaNbO3 perovskite. A stable dielectric constant over a temperature range from 25-200{\deg}C, low dielectric losses less than 0,03, and excellent frequency stability at room temperature were obtained. The decrease in niobium content promoted TTB crystallization with the improvement of the high dielectric properties of the system. The optimum of the dielectric constant and recoverable energy storage density were obtained for BNP41 crystallized at 1000{\deg}C. Analyses of the complex impedance indicated that the niobium content and crystallization temperature affect the interfacial polarization., Comment: 10 pages, 11 figures, 3 tables

Barium sodium niobate Ba$_2$NaNb$_5$O$_{15}$ (BNN) ceramics with different amounts of BaO-Na$_2$O-Nb$_2$O$_5$-P$_2$O$_5$ (BNNP) glass were prepared via the conventional solid-state method. The effect of glass content on the structural, microstructure, and dielectric properties of BNN ceramics was investigated. The XRD results showed that no secondary phase was formed after adding BNNP glass. It was found that such additions reduce the average grain size and refine the microstructure of the obtained ceramics. Moreover, the samples exhibited a stable dielectric constant over the temperature range of 25$^\circ$C-150$^\circ$C, and their dielectric constants were significantly improved. The ceramic with 7.5 wt% BNNP glass content showed a dielectric constant which is more than twice as much as that of pure BNN ceramic, as well as a low dielectric loss of less than 5%., Comment: 5 pages, 5 figures

Multiferroic CoFe2O4-Ba0.95Ca0.05Ti0.89Sn0.11O3 core-shell nanofibers (CFO@BCTSn NFs) were synthesized by a sol-gel co-axial electrospinning technique. The scanning electron microscope and transmission electron microscope were used to check nanofibers' core-shell structure/configuration. X-ray diffraction and a high-resolution transmission electron microscope were used to confirm the spinel structure of CFO and the perovskite structure of BCTSn. The magnetic character of the resultant CFO@BCTSn NFs was determined by SQUID magnetometry. The piezoelectricity was verified using piezo-response force microscopy, which revealed an entirely covered ferroelectric shell outline, in accordance with SEM and TEM observations. The magnetoelectric (ME) coefficient was measured as a function of the applied external DC magnetic field. The maximum ME coefficient obtained for the CFO@BCTSn NFs was 346 mV cm-1 Oe-1. The high magnetoelectric coupling suggests that CFO@BCTSn NFs could be a promising candidate for magnetic field sensor and magnetoelectric device applications.

Multiferroic particulate composites $(1-x)$ Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$-$(x)$CoFe$_2$O$_4$ with ($x$ = 0.1, 0.2, 0.3, 0.4 and 0.5) have been prepared by mechanical mixing of the calcined and milled individual ferroic phases. X-ray diffraction and Raman spectroscopy analysis confirmed the formation of both perovskite Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$ (BCTSn) and spinel CoFe$_2$O$_4$ (CFO) phases without the presence of additional phases. The morphological properties of the composites were provided by using Field Emission Scanning Electron Microscopy. The BCTSn-CFO composites exhibit multiferroic behavior at room temperature, as evidenced by ferroelectric and ferromagnetic hysteresis loops. The magnetoelectric (ME) coupling was measured under a magnetic field up to 10 kOe and the maximum ME response found to be 0.1 mV /cm/ Oe for the composition 0.7 BCTSn-0.3 CFO exhibiting a high degree of pseudo-cubicity and large density.

The electrocaloric (EC) effect and energy storage properties of eco-friendly ferroelectric Ba0.9Sr0.1Ti1-xSnxO3 (BSTS-x) ceramics prepared by the conventional solid-state reaction method were studied. Significant energy efficiency exceeding 80% was found in our samples. In particular, BSTS-5 and BSTS-10 samples exhibit 92% and 88% efficiency, respectively, over a wide temperature range around room temperature (RT). Direct EC measurement and an indirect method based on the thermodynamic approach were used to characterize the EC effect, and both yielded consistent results. The largest electrocaloric responsivity of 0.73 K mm/kV was obtained for BSTS-0 at 368 K with an adiabatic temperature change DT(EC) of 0.55 K at a low applied electric field of only 7.4 kV/cm. With increasing Sn-content, the EC response of BSTS-x ceramics decreases, while their diffuseness increases over an extensive temperature range, centered at RT. A significant coefficient of performance (COP > 26) was found for our samples. The obtained results demonstrate the possibility of designing eco-friendly materials with higher EC effect and energy efficiency for potential solid-state refrigeration and energy storage devices.

Lead-free ba0.85ca0.15zr0.1ti0.9o3 (bczt) ceramic powders were synthesized using the sol-gel method. to achieve high-energy storage and large electrocaloric effect in bulk ceramics the ceramics thickness was reduced. dielectric, ferroelectric, energy storage, and electrocaloric properties were investigated for bczt ceramic with 400 {\mu}m. here, pure crystalline structure and homogenous microstructure were identified by xrd analysis and sem measurements, respectively. the dielectric measurements revealed a maximum dielectric constant associated with ferroelectric-paraelectric phase transition. the maximum of {\epsilon} was 7841 around 352 k. furthermore, the bczt ceramic showed improved energy storage and electrocaloric properties. a high recoverable energy density wrec of 0.24 j/cm3 and a total energy density wtotal of 0.27 j/cm3 with an efficiency coefficient of ~ 88% at 423 k under an electric field of 55 kv/cm was obtained. besides, the maximum value of {\delta}t = 2.32 k, the electrocaloric responsivity {\zeta} = 0.42 k mm/kv, the refrigeration capacity rc= 4.59 j/kg and the coefficient of performance cop = 12.38 were achieved around 384 k under 55 kv/cm. the total energy density wtotal and the temperature change {\delta}t were also calculated by exploiting the landau-ginzburg-devonshire (lgd) theory. the theoretical results matched the experimental findings. these results suggest that the synthesized bczt ceramic with the reduced thickness could be a promising candidate for energy storage and electrocaloric applications.

This work focuses on the microstructure, magnetic properties and magnetocaloric effect of CoFe$_2$O$_4$ (CFO) nanoparticles elaborated by sol-gel auto combustion method. The XRD investigation indicates that CFO is crystallized in a cubic spinel structure and the SEM micrograph shows a fine quasi-spherical with an average grain sizes of 160 nm. The temperature dependence of the Raman spectra reveals the ferromagnetic to paramagnetic (FM-PM) transition started from 723 K and the magnetization versus temperature measurements shows the Curie temperature located at T$_{\rm C}$ = 785 K. Large value of magnetocaloric temperature change of $\Delta$T =11.2 K with a high RCP of 687.56 J Kg$^{-1}$ are achieved indirectly via the Maxwell approach making our CFO nanopowder suitable candidate for both environmentally friendly magnetic refrigeration and medical applications at ambient temperature.

Structural, dielectric, ferroelectric, energy storage properties, and electrocaloric effect were studied in lead-free ceramic Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$ (BCTSn) elaborated by sol-gel method. Phase purity structure was confirmed from X-ray data using Rietveld refinement analysis which revealed the coexistence of tetragonal (P4mm) and orthorhombic (Amm2) symmetries at room temperature. Phase transitions were detected by dielectric and differential scanning calorimetry results. Energy storage properties were determined from P-E hysteresis, and the electrocaloric properties were calculated indirectly via the Maxwell approach. The large value of electrocaloric temperature change of $\Delta$T=0.807 K obtained at a relatively small field of 30 kV cm$^{-1}$ and high energy storage efficiency can make BCTSn ceramic a promising candidate for environmentally friendly refrigeration and energy storage applications.

Strain engineering is a powerful mean for tuning the various functionalities of ABO3 perovskite oxide thin films. Rare-earth orthoferrite RFeO3 materials such as NdFeO3 (NFO) are of prime interest because of their intriguing magnetic properties as well as their technological potential applications especially as thin films. Here, using a large set of complementary and advanced techniques, we show that NFO epitaxial thin films, successfully grown by pulsed laser deposition on (001)-SrTiO3, show a strong magnetic anisotropy below a critical thickness tc of 54 nm, associated with the occurrence of structural modifications related to symmetry and domain pattern changes. By varying the tensile misfit strain through the decrease of film thickness below tc, the amplitudes of in and out-of-plane magnetization can be continuously tuned while their ratio stays constant. Furthermore, different low-temperature magnetic behaviors are evidenced for strained and relaxed films, suggesting that the strain-induced structural state impacts the magnetic phase stability.

Rare-earth orthoferrite RFeO3 materials such as NdFeO3 are strongly studied because of their fascinating magnetic properties and their potential applications. Here, we show the successful epitaxial synthesis of parasitic-free NFO thin film by pulsed laser deposition on (001)-SrTiO3. High-resolution X-ray diffraction shows a coherent growth and a tetragonal-like structure of a tensile strained 80 nm thick NFO film in contrast with the bulk orthorhombic state. Room temperature magnetometry indicates a bulk-like antiferromagnetic state for the NFO film. Temperature-dependent X-ray diffraction and magnetometry highlight a significant spin-lattice coupling at the Neel Temperature while a new magneto-structural instability is discovered around 250{\deg}C that needs further investigation.

Antiferroelectrics are promising materials for high energy density capacitors and the search for environmentally-friendly and efficient systems is actively pursued. An elegant strategy to create and design new (anti)ferroic system relies on the use of nanoscale superlattices. We report here the use of such strategy and the fabrication of nanoscale BiFeO3/NdFeO3 superlattices and in depth characterization using high resolution X-ray diffraction and Transmission Electron Microscopy. The structural analysis at atomic scale demonstrates that such superlattices host anti-polar ordering most likely described by an antiferroelectric-like Pbnm symmetry. Temperature dependence of anti-polar state and structural transition further hint that the stability of the anti-polar state is controlled by the BiFeO3 layer thickness within the stacking and, in a more moderate way, by interlayer strain. Discovery of such polar arrangement in superlattices and the possible generalization to the whole rare-earth family pave the way to new platforms for energy storage application as well as nano-electronic devices.

Na$_{0.5}$(Bi$_3$/4RE$_{1/4}$)$_{0.5}$TiO$_3$ (RENBT, RE = Nd, Gd, Dy, and Ho) compounds were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave (FP-LAPW) method based on the spin-polarized density functional theory implemented in the WIEN2k code. Combined charge density distribution and Ti K-edge x-ray absorption spectra revealed that the RENBT compositions with high polarization values were accompanied by a higher TiO$_6$ distortion, DyNBT, and NdNBT compounds. The effect of the rare-earth elements on the polarization were confirmed experimentally with the collection of the hysteresis loops. The investigation of the electronic properties of the compounds highlighted the emergence of a magnetization owing to the 4f orbital effect of the rare-earth elements. Besides, the investigation of the chemical ordering showed a short-range chemical ordering for the pure composition and an increased A-site disorder for dysprosium doped NBT system. The increased disorder may speak for increased relaxor properties in the RE doped compositions., Comment: arXiv admin note: text overlap with arXiv:2003.03978

In this work structural refinement, complex impedance spectroscopy, and Raman spectroscopy have been investigated on Na$_{0.5}$(Bi$_{1-x}$Dy$_x$)$_{0.5}$TiO$_3$ (xDyNBT) ceramic systems. The pure NBT, 2DyNBT and 5DyNBT compounds crystallize in a rhombohedral structure while the 15DyNBT composition crystallizes in an orthorhombic Pnma structure. We reported that dysprosium addition affects the phase transition temperatures as well as the dielectric losses. The electrical transport at high temperatures was investigated using the CIS over a wide frequency range. The studied samples showed a non-Debye type process, with a short-range relaxation for the pure NBT and a coexistence of both localized and long-range relaxations of charge carriers for the 2DyNBT and 5DyNBT compounds. For the high concentration, 15DyNBT, a short-range relaxation is observed. Moreover, using a brick-layer model we discuss the resistance and capacitance of the different contributors (grain and grain boundaries) in our samples. High temperature Raman spectroscopy investigation was performed in order to follow the temperature evolution of the structural transformations on ferroelectric compounds. Anomalies in the temperature evolution of the vibrational modes are seen to correlate well with the temperature transitions observed from dielectric measurements.

A-site deficient Ba$_{0.975}$La$_{0.017}$(ZrxTi$_{0.95-x}$)Sn$_{0.05}$O$_3$ (x = 0.05; 0.20) ceramics (BLaZ100xTS) were synthesized using the solid-state reaction. The microstructural study revealed a high density and low porosity in the studied ceramics. Besides, grain size lower than 1.5 micrometer was observed in the studied compounds, which is due to the incorporation of the rare earth element (lanthanum). X-ray diffraction and Raman studies revealed that BLaZ5TS and BLaZ20TS crystallize in a perovskite-type structure with tetragonal and cubic symmetry, respectively. The dielectric study showed a normal ferroelectric-paraelectric phase transition for BLaZ5TS while a diffuse phase transition is noticed for BLaZ20TS sample. The energy-storage density and the associated energy efficiency were determined from the P-E loops versus temperature and the calculated values are comparable with results obtained on BCZT systems. Furthermore, the adiabatic temperature change (Delta)T was calculated through the indirect method and a relatively high value of (Delta)T/(Delta)E = 0.2 10-6 K m/V is obtained in BLaZ5TS system. The simultaneous presence of energy storage property and electrocaloric responsivity makes this system a promising environmentally friendly candidate for application in electronic devices.

In this work we elaborated and characterized nanocomposite thin films using a preselected multiferroic matrix Bi$_{0.9}$Gd$_{0.1}$Fe$_{0.9}$Mn$_{0.1}$O$_3$ (BGFMO) in the aim to enhance their basic ferroelectric and magnetic properties. The local ferroelectric character of these nanocomposites thin films was investigated by piezoresponse force microscopy (PFM). Switching behavior for ferroelectric domains was probed by locally manipulating domains. The magnetic investigation showed that the incorporation of transition metal elements in the BGFMO matrix brings out interesting increase in the macroscopic magnetisation at room temperature. Moreover, a spin glass type behavior is observed in M(T) curves for the studied thin films.

Lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) ceramics have demonstrated excellent dielectric, ferroelectric and piezoelectric properties in comparison to lead-based materials. The synthesis of pure and crystalline BCZT nanopowders at low temperatures of 25, 80 and 160 C was reported previously by using a sol-gel method followed by a hydrothermal route. In this study, the structural, dielectric and ferroelectric properties of sintered BCZT ceramics at 1250 {\deg}C for 10h were investigated. XRD measurements revealed the presence of a single perovskite phase at room temperature with the coexistence of the orthorhombic and tetragonal symmetries. The increase of grain size and the ceramic density in BCZT ceramics result in an enhancement of the dielectric and ferroelectric properties of BCZT ceramics. More interestingly, the synthesis temperature of BCZT powders with high dielectric and ferroelectric properties could be decreased to a low temperature of 160 {\deg}C, which is about 1200 {\deg}C lower when compared with solid-state reaction and 840 {\deg}C lower when compared with sol-gel methods. The BCZT ceramics elaborated at 160 {\deg}C revealed excellent electrical properties. Hence, the use of low-temperature hydrothermal processing can be encouraging for the synthesis of lead-free ceramics with high dielectric and ferroelectric properties.

The chemical ordering, electrical, optical, and magnetic properties of $Na_{0.5}Bi_{0.5}TiO_{3}$ (NBT) and 25$\%$ dysprosium doped NBT (DyNBT) were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave (FP-LAPW) method based on spin-polarized density functional theory implemented in the WIEN2k code. We demonstrated that NBT structure is stable in the 001 A-site configuration, while DyNBT presents an A-site disorder perceived by the minimal energy difference between the different A-site configurations. A significant magnetic moment of $5{\mu}B$ emerges in DyNBT system, while NBT is known to be non-magnetic. Dysprosium in NBT matrix seems to form an ionic bonding with oxygen atoms whereas Bi-O forms covalent bonding which is responsible for the decrease of the polarization value from 42.3 ${\mu}C/cm^{2}$ for NBT to 22.08 ${\mu}C/cm^{2}$ for the doped compound. In the second part, the transition temperature and the hysteresis loops of $Na_{0.5}(Bi_{1-x}Dy_{x})_{0.5}TiO_{3}$ system x = 0 - $25\%$ were investigated using the Monte Carlo simulation. We observed a decrease in the transition temperature as a function of dysprosium introduction. We pointed out from the hysteresis loops, an apparent decrease of the coercive field together with the remanent polarization as a function of doping and also as a function of temperature. Our proposed model was seen to approach the values of experimental studies.

The magnetic properties of a novel cobalt-based hydrogen vanadate, Co13.5(OH)6(H0.5VO3.5)2(VO4)6, are reported. This new magnetic material was synthesized in single-crystal form using a conventional hydrothermal method. Its crystal structure was determined from single-crystal X-ray diffraction data and was also characterized by scanning electron microscopy. Its crystal framework has a dumortierite-like structure consisting of large hexagonal and trigonal channels; the large hexagonal channels contain one-dimensional chains of face-sharing CoO6 octahedra linked to the framework by rings of VO4 tetrahedra, while the trigonal channels are occupied by chains of disordered V2O4 pyramidal groups. The magnetic properties of this material were investigated by DC magnetic measurements, which indicate the occurrence of antiferromagnetic interactions.

A novel alluaudite type vanadate has been successfully synthesized in its single crystal and polycrystalline forms. Its crystal structure was determined by means of X ray diffraction measurements. This new vanadate crystallizes in monoclinic system. The crystal structure of this vanadate displays an open transition metals based framework enclosing two kind of tunnels where the sodium cations are located. Moreover, the purity of the obtained powder was confirmed by X ray powder diffraction analysis. Furthermore, this new vanadate was characterized by scanning electron microscopy, Infrared spectroscopy and by magnetic measurements. The magnetic susceptibility showed the antiferromagnetic behavior of this vanadate with negatve Curie- Weiss temperature consistently with the expected magnetic interactions between iron cations.

Single crystals of a new silver and-cobalt based vanadate AgCo2V3O10 were grown from a melted mixture. The crystal structure determination reveals that this new vanadate crystallizes in triclinic system with space group P-1. The structure of the titled compound is constructed from CoO6octahedra and VO4 tetrahedra sharing edges and vertices leading to an open three-dimensional framework delimiting tunnels along [001], where the Ag cations are located. The bands observed in Raman spectrum were assigned to corresponding vibrations of the VO4 groups. DC and AC magnetization (susceptibility) measurements revealed the spin-glass (SG) -type transition below a frequency-independent temperature Tf(H) that is nearly independent on the applied magnetic field. Magnetic field H> 10 kOe induces the spin glass antiferromagnet. These observations brings AgCo2V3O10 into the class of geometrically frustrated magnetic systems.

Ferroelectric glass-ceramics are promising composite materials with dual properties, of high dielectric permittivity and high dielectric breakdown strength. In this context, new phosphate glass-ceramics 2BaO-0.5Na2O 2.5[(1-x)Nb2O5 xWO3]-1P2O5 (x=0, 0.1, 0.2, 0.3 and 0.4) designated as B0, B1, B2, B3, B4 respectively, were prepared by the controlled crystallization technology and then crystallized at high temperature of 760 {\deg}C for 10 hours. Subsequently, the obtained glass-ceramics were studied by Differential Scanning Calorimetry (DSC), X-ray powder diffraction (XRD), Raman, impedance spectroscopy, and the P-E hysteresis loops. All of these techniques allowed the identification of Ba2Na4W2Nb8O30 phase with tungsten bronze structure embedded in the glassy matrix. The density of glass-ceramics was found to increase with increasing tungsten content to reach a maximum at x =0.3 and then decreases. Dielectric and conductivity parameters were found to be governed by the presence of oxygen vacancies. Room temperature energy storage property which depends on the composition X, was performed using P-E hysteresis loops of the glass-ceramics. The optimum discharge density was obtained for B3 with an energy efficiency of 73.77%., Comment: 19 pages, 9 figures

By using the semi-wet synthesis method, lead-free ferroelectric materials Ba0.9Sr0.1Ti1-xSnxO3 with x = 0, 0.02, 0.05, and 0.10 (abbreviated as BSTS) were prepared and their structural, electric and electrocaloric properties were investigated. The X-ray diffraction (XRD) patterns show that the samples calcined at 950{\deg}C have well crystallized into perovskite structure suggesting the substitution of Ti4+ by Sn4+ in BST lattice. With increasing content of Sn, the enhancement of the dielectric permittivity was observed for (0

Lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) ceramic exhibits excellent dielectric, ferroelectric and piezoelectric properties at the Morphotropic Phase Boundary (MPB). Previously, we demonstrated that the use of the anionic surfactant Sodium Dodecyl Sulfate (SDS, NaC12H25SO4) could enhance the dielectric properties of BCZT ceramic using surfactant-assisted solvothermal processing [1]. In the present study, structural, dielectric, ferroelectric properties, as well as electrocaloric effect and energy storage performances of this BCZT ceramic were thoroughly investigated. X-ray diffraction (XRD) measurements revealed the presence of single perovskite phase at room temperature with the coexistence of orthorhombic and tetragonal symmetries. In-situ Raman spectroscopy results confirmed the existence of all phase transitions from rhombohedral through orthorhombic and tetragonal to cubic symmetries when the temperature varies as reported in undoped-BaTiO3. Evolution of energy storage performances with temperature have been investigated. BCZT ceramic exhibits a high energy storage efficiency of ~80% at 120 {\deg}C. In addition, the electrocaloric responsivity was found to be 0.164.10-6 K.m/V at 360 K.

Photovoltaic (PV) response of epitaxial BiFe0.95Mn0.05O3 thin film grown by pulsed laser deposition has been investigated on a broad range of temperature. Wavelength dependent photovoltaic effect shows the contribution of in gap level states most likely connected to the manganese doping on the B-site of the perovskite unit cells and presence of defects (Bi and O vacancies). The temperature dependent response of the PV response rules out electromigration and/or Schottky barriers as dominant mechanisms. This is corroborated with the observed switchable photovoltaic effect that can be explained either by the depolarizing field or bulk photovoltaic effect. In addition the PV response shows strong correlation with the low temperature polaronic like conduction mechanism and high open circuit voltage (2.5V) is detected in the investigated vertical capacitive geometry.