Correction: Enhanced electrocaloric effect, energy storage density and pyroelectric response from a domain-engineered lead-free BaTi0.91Sn0.08Zr0.01O3 ferroelectric ceramic.

[This corrects the article DOI: 10.1039/D2RA04914G.].

Effect of frequency on the classical and relaxor ferroelectric behavior of substituted titanate Ba0.7Er0.16Ca0.05Ti0.91Sn0.09O3.

In the present work, we synthesized the perovskite Ba0.70Er0.16Ca0.05Ti0.91Sn0.09O3 compound (BECTSO) by a solid-state reaction and sintering at 1200 °C. The effects of doping on the structural, electrical, dielectric, and ferroelectric characteristics of the material are examined in this work. X-ray powder diffraction analysis shows that BECTSO crystallizes in a tetragonal structure with space group P4mm. A detailed study of the dielectric relaxation of the BECTSO compound has been reported for the first time. Classical low-frequency ferroelectric and high-frequency relaxor ferroelectric behaviors have been studied. The study of the real part of the permittivity (ε') as a function of temperature demonstrated a high dielectric constant and identified a phase transition from the ferroelectric phase to the paraelectric phase at Tc = 360 K. The analysis of conductivity curves shows two behaviors: semiconductor behavior for f < 106 Hz and metallic behavior for f >106 Hz. The relaxation phenomenon is dominated by the short-range motion of the charge carriers. The BECTSO sample could be considered as a potential lead-free material for next-generation non-volatile memory devices and wide-temperature range capacitor applications.

Magnetocaloric effect and critical behavior of the La0.75Ca0.1Na0.15MnO3 compound.

In this paper, we have studied the critical behavior and the magnetocaloric effect (MCE) simulation for the La0.75Ca0.1Na0.15MnO3 (LCNMO) compound at the second order ferromagnetic-paramagnetic phase transition. The optimized critical exponents, based on the Kouvel-Fisher method, were found to be: ß = 0.48 and γ = 1. These obtained values supposed that the Mean Field Model (MFM) is the proper model to analyze adequately the MCE in the LCNMO sample. The isothermal magnetization M(H, T) and the magnetic entropy change -ΔSM(H, T) curves were successfully simulated using three models, namely the Arrott-Noakes equation (ANE) of state, Landau theory, and MFM. The framework of the MFM allows us to estimate magnetic entropy variation in a wide temperature range within the thermodynamics of the model and without using the usual numerical integration of Maxwell relation.

Enhanced electrocaloric effect, energy storage density and pyroelectric response from a domain-engineered lead-free BaTi0.91Sn0.08Zr0.01O3 ferroelectric ceramic.

A BaTi0.91Sn0.08Zr0.01O3 (BTSZ) ceramic was prepared by a conventional solid-state reaction method. Its structural, dielectric, ferroelectric, and pyroelectric properties were carefully studied. The Rietveld refinement was used to characterize the structural proprieties of the synthesized ceramic. The microstructure was observed by scanning electron microscopy. Phase transitions observed in the temperature dependent dielectric permittivity (ε r-T and tan δ-T) showed a transition close to room temperature, resulting in improved piezoelectric, pyroelectric and electrocaloric performance. In addition, it was found that an electric field poling process changed the character of ε r-T and tan δ-T plots. Resonance modes in the polarized state, where maximum power transmission was achieved, were observed in the impedance spectrum. The extra-slim hysteresis loops revealed a relatively low coercive field and hysteresis loss related to the diffuse phase transition, which can significantly improve energy storage efficiency up to 75% at 100 °C. To characterize the electrocaloric effect (ECE), indirect and direct methods based on the thermodynamic approach were used. Both methods results showed good consistency and revealed a large ECE peak evolving along the phase diagram. Furthermore, pyroelectric figures of merit (FOMs) for voltage responsivity (F v), current responsivity (F i), energy harvesting (F E), new energy harvesting and detectivity (F d) were calculated. Finally, thermal energy harvesting (N D) was determined by using the Olsen cycle. The obtained maximum N D was 233.7 kJ m-3 when the Olsen cycle operated at 25-100 °C and 0-30 kV cm-1. This study introduces not only a technique to produce a high performance ceramic for refrigeration devices, but also broadens the range of applications for BT-based lead-free ferroelectrics beyond actuators, sensors, and energy harvesting to solid-state cooling.

Evaluation of the microstructure, optical properties and hopping conduction mechanism of rare earth doped Ba0.85Ca0.12RE0.03Ti0.90Zr0.04Nb0.042O3 ceramics (RE = Ce3+ and Pr3+).

The current research work examines the impact of Rare Earth (RE3+) ion substitution on the structural, optical and conduction properties of a Ba0.85Ca0.12RE0.03Ti0.90Zr0.04Nb0.042O3 (BCRETZN) (RE = Ce, Pr) ceramic compound produced via a solid-state route. The Rietveld method of the X-ray data revealed a tetragonal (P4mm) structure at room temperature for our ceramic compound. The morphology of the compound was explored using Scanning Electron Microscopy (SEM) as well as optical response and conduction behavior. The photoluminescence properties revealed that the BCPrTZN sample results in green and red photoemissions under laser excitation at 450 nm at RT. Furthermore, for the BCCeTZN sample, the photoluminescence data demonstrated that strong violet emission bands were acquired, at RT upon an excitation at 350 nm. The electrical conduction process was verified via the correlated barrier Hopping method. The scaling behavior suggests that the electrical conduction mechanism is independent of temperature. The existence of Ce3+ and Pr3+ ions in these materials could have important technological potential in new multifunctional devices.

Structural and morphological studies, and temperature/frequency dependence of electrical conductivity of Ba0.97La0.02Ti1-x Nb4x/5O3 perovskite ceramics.

Conductivity measurements of our polycrystalline perovskite ceramic systems with a composition of Ba0.97La0.02Ti1-x Nb4x/5O3 (x = 5, 7 and 10, in mol%) were performed, in order to investigate frequency and temperature dependence. Our ferroelectric ceramics were fabricated by the molten-salt method (chemical reaction followed by an evaporation and filtration reaction); X-ray diffraction patterns indicated that a single phase was formed for pure BaLT1-x Nb4x/5 ceramics. The electrical behavior of the ceramics was studied by impedance spectroscopy in the 500-610 K temperature range. The conductivity was investigated which can be described by the Jonscher law. Both AC and DC electrical conductivities are completely studied as a function of frequency and temperature. The conductivity exhibits a notable increase with increasing Nb-rates. The low-frequency conductivity results from long-range ordering (close to frequency-independent) and the high-frequency conductivity is attributable to the localized orientation hopping process. Impedance analysis was performed revealing conductivity data which fitted the modified power, σ AC(ω) = Aω n . The frequency dependence of the conductivity plot has been found to obey the universal Jonscher power law. Both AC and DC electrical conductivities are thoroughly studied as a function of frequency as well as temperature. The AC conductivity reveals that correlated barrier hopping (CBH) and non-overlapping small polaron tunneling (NSPT) models are suitable theoretical models to elucidate the conduction mechanisms existing in our compounds. Significantly, by increasing the temperature, the DC conductivity was increased, which verifies the semiconducting nature of the materials.

Raman scattering and red emission of Mn4+ in La0.7Sr0.25Na0.05Mn0.7Ti0.3O3 manganite phosphor for LED applications.

The vibrational and optical properties of an La0.7Sr0.25Na0.05Mn0.7Ti0.3O3 (LSNMT) polycrystalline sample produced via a solid-state reaction were studied. The Raman spectrum at room temperature reveals the chemical disorder in our compound. The optical gap and Urbach energy were estimated on the basis of the absorption spectrum. Moreover, the polycrystalline manganite radiates in the near-infrared light (1000 nm) with 514.5 nm light excitation and in the temperature range from 10 K to 300 K. Crystal field analysis suggests that only the Mn4+ luminescent center is found in LSNMT. The measured activation proves that our compound possesses good thermostability. The chromaticity coordinates prove that the emission of the LSNMT sample occurs in the near-infrared region. All analytical findings demonstrate that LSNMT manganite has substantial prospective applications in white luminescent devices.

The structure and photoluminescence of a ZnO phosphor synthesized by the sol gel method under praseodymium doping.

This work outlines some interesting results regarding the effects of Pr3+ substitution on the structural and optical properties of (x = 0 and 0.02) samples. Our samples were synthesized using the Pechini sol-gel method. The structural study using Rietveld refinement of XRD patterns showed a hexagonal structure with the P63mc space group for all the samples and also the existence of a secondary phase attributed to the praseodymium oxide (Pr6O11) for 2% wt Pr-doped ZnO. The refinement results revealed that both the lattice parameter and the unit cell volume increase with the increase of Pr content. X-ray peak broadening analysis was used to evaluate the crystallite size and lattice strain by the Williamson-Hall (W-H) method and size-strain plot method (SSPM). The physical parameters such as strain, stress and energy density values were also calculated using the W-H method with different models, namely uniform deformation model (UDM), uniform stress deformation model (USDM) and uniform deformation energy model (UDEDM). The obtained results showed that the mean particle size of the ZnO and Pr0.01Zn0.97O estimated from W-H analysis and the SSPM method are highly intercorrelated. Shifting of the absorption edge to lower wavelength and blue shift of the band gap are observed in the UV-visible spectra of Pr-doped ZnO samples. Particular emphasis was put on the PL measurements of such composites. A noticeable decrease of the maximum intensity of PL response was found after adding Pr3+ to ZnO. This finding is discussed in terms of the photo excited limitation of electron-hole pairs in such nanocomposites.

Influence of defect on the electrical and optical properties of A-site non-stoichiometry Ca0.67La0.22□0.11Ti(1-x)Cr x O3-δ perovskite.

An investigation of the dielectric dispersion, electrical properties, scaling behavior and optical defects of Ca0.67La0.22□0.11Ti(1-x)Cr x O3-δ (CLT(1-x)Cr x ) with x = 0 and x = 0.1 compositions is presented. The square in the formula is attributed to a vacancy in A-site. Relaxation phenomena were studied with dielectric and modulus formalism, while, the conductivity mechanism was investigated using electrical conductivity. A high permittivity of around 104, low dielectric loss and low electrical conductivity of around 10-3 S cm-1 for Ca0.67La0.22TiO3 (CLT) was observed. These values make this composition interesting for microelectric applications. A comparison between the Z'' and M'' indicated that the short-range carrier motion dominates at low temperature and becomes less localized at high temperature. The optical defects of CLT and Ca0.67La0.22Ti0.9Cr0.1O3 (CLT0.9Cr0.1) were studied by electron paramagnetic resonance (EPR) spectroscopy. The results suggest the formation of a [TiO6]9- center, a (Ti3+-V O) center, and dipole defect for CLT compound and Cr3+-V O center defect for CLT0.9Cr0.1 compound. These defects are the source of the in-gap electron traps, which improve the optical properties of CLT(1-x)Cr x and hence make it an interesting optical material for different applications.

Critical behavior near room temperature in La0.75Ca0.05Na0.20MnO3 sample.

The critical behavior of La0.75Ca0.05Na0.20MnO3 was studied at around room temperature via magnetization measurements. From the relative slope, we deduced that the Tricritical Mean-Field model was the most suitable model. The estimated critical exponents were found to be ß = 0.24 ± 0.004, γ = 0.98 ± 0.065 and δ = 5.08 at T C = 300 K. These critical exponents satisfied the Widom scaling relation δ = 1 + γ/ß, implying the reliability of our values. Based on the critical exponents, the magnetization-field-temperature (M-µ 0 H-T) data around T C collapsed into two curves, obeying the single scaling equation with ε = (T - T C)/T C being the reduced temperature. These results suggest short-range interaction in our sample.

Study of diffuse phase transition and relaxor ferroelectric behavior of Ba0.97Bi0.02Ti0.9Zr0.05Nb0.04O3 ceramic.

In the present work, structural and dielectrics properties of polycrystalline sample Ba0.97Bi0.02Ti0.9Zr0.05Nb0.04O3 (BBTZN) prepared by a molten-salt method were investigated. X-ray diffraction analyses revealed the formation of a single-phase pseudocubic structure with a Pm3̄m space group. Unlike the trend observed in classic ferroelectrics, the temperature dependence of the dielectric constants showed the presence of three sequences of structural phase transitions. In fact, the local disorder provides a frequency dependent relaxor like behaviours attributed to the dynamic of polar nanoregions (PNRs). The diffuse phase transition (DPT) analyzed using the modified Curie-Weiss law and Lorenz formula confirms the presence of short-range association between the nanopolar domains. The obtained values of the degree of diffuseness are found to be in the range of 1.58-1.78 due to the existence of different states of polarization and, hence, different relaxation times in different regions. The frequency dependence of temperature at dielectric maxima, which is governed by the production of PNRs at a high temperature, satisfies the Vogel-Fulcher (V-F) law. The temperature dependence of the electric modulus for various frequencies indicating a thermally activated relaxation ascribed to the Maxwell-Wagner (M-W) space charge relaxation phenomenon.

Large magnetocaloric entropy change at room temperature in soft ferromagnetic manganites.

In this paper, La0.75Ca0.25-x Na x MnO3 (x = 0.15 and 0.20) samples were prepared by the flux method. Crystallographic study revealed that the x = 0.15 sample is characterized by the coexistence of a mixture of orthorhombic and rhombohedral structures with Pbnm and R3̄c space groups, respectively. While, the x = 0.20 sample crystallized in the rhombohedral structure with a R3̄c space group. Magnetic data, under a magnetic field of 0.05 T, indicated that our samples undergo a ferromagnetic (FM)-paramagnetic (PM) phase transition, on increasing the temperature. The magnetic field dependence of the magnetocaloric properties of La0.75Ca0.25-x Na x MnO3 (x = 0.15 and 0.20) samples, with the second phase transition, was investigated. Near room temperature, the x = 0.20 sample exhibited a large magnetic entropy change with maxima of 6.01 and 3.12 J kg-1 K-1, respectively, under applied magnetic fields of 5 and 2 T. Also, the relative cooling power (RCP) was calculated. According to hysteresis cycles, for our studied samples, at 10 K a typical soft FM behavior with a low coercive field was observed. These results make our samples promising candidates for magnetic refrigerators, magnetic recording, and memory devices.

Frequency and temperature-dependence of dielectric permittivity and electric modulus studies of the solid solution Ca0.85Er0.1Ti1-x Co4x/3O3 (0 ≤ x ≤ 0.1).

The dielectric properties of Ca0.85Er0.1Ti1-x Co4x/3O3 (CETCo x ) (x = 0.00, 0.05 and 0.10), prepared by a sol-gel method, were systematically characterized. The temperature and frequency dependence of the dielectric properties showed a major effect of the grain and grain boundary. The dielectric constant and dielectric loss of CETCo x decreased sharply with increasing frequency. This is referred to as the Maxwell-Wagner type of polarization in accordance with Koop's theory. As a function of temperature, the dielectric loss and the real part of permittivity decreased with increasing frequency as well as Co rate. Indeed, a classical ferroelectric behavior was observed for x = 0.00. The non-ferroelectric state of the grain boundary and its correlation with structure, however, proved the existence of a relaxor behavior for x = 0.05 and 0.10. The complex electric modulus analysis M*(ω) confirmed that the relaxation process is thermally activated. The normalized imaginary part of the modulus indicated that the relaxation process is dominated by the short range movement of charge carriers.

Critical phenomena and estimation of the spontaneous magnetization from a mean field analysis of the magnetic entropy change in La0.7Ca0.1Pb0.2Mn0.95Al0.025Sn0.025O3.

In the present work, we have studied the universal critical behavior in the perovskite-manganite compound La0.7Ca0.1Pb0.2Mn0.95Al0.025Sn0.025O3. Experimental results revealed that all samples exhibit a second-order magnetic phase transition. To study the critical behavior of the paramagnetic-ferromagnetic transition, various techniques such as modified Arrott plots, the Kouvel-Fisher method and critical isotherm analysis were used to determine the values of the Curie temperature T C, as well as the critical exponents ß (corresponding to the spontaneous magnetization), γ (corresponding to the initial susceptibility) and δ (corresponding to the critical magnetization isotherm). The critical exponent values for our sample are consistent with the prediction of the mean field model (ß = 0.46, γ = 1.0, and δ = 2.94 at an average T C = 302.12 K), indicating that the magnetic interactions are long-range. The reliability of the critical exponent values was confirmed by the Widom scaling relation (WSR) and the universal scaling hypothesis. Moreover, to estimate the spontaneous magnetization of La0.7Ca0.1Pb0.2Mn0.95Al0.025Sn0.025O3 perovskite, we used the magnetic entropy change (ΔS M), obtained from isothermal magnetization. The results obtained through this approach are compared to those obtained from classical analysis using Arrott curves. An excellent agreement is found between this approach and the one obtained from the extrapolation of the Arrott curves.

Large magnetic entropy change and prediction of magnetoresistance using a magnetic field in La0.5Sm0.1Sr0.4Mn0.975In0.025O3.

A detailed study of the structural, magnetic, magnetocaloric and electrical effect properties in polycrystalline manganite La0.5Sm0.1Sr0.4Mn0.975In0.025O3 is presented. The X-ray diffraction pattern is consistent with a rhombohedral structure with R3̄c space group. Experimental results revealed that our compound prepared via a sol-gel method exhibits a continuous (second-order) ferromagnetic (FM) to paramagnetic (PM) phase transition around the Curie temperature (T C = 300 K). In addition, the magnetic entropy change was found to reach 5.25 J kg-1 K-1 under an applied magnetic field of 5 T, corresponding to a relative cooling power (RCP) of 236 J kg-1. We have fitted the experimental data of resistivity using a typical numerical method (Gauss function). The simulation values such as maximum resistivity (ρ max) and metal-semiconductor transition temperature (T M-Sc), calculated from this function, showed a perfect agreement with the experimental data. The shifts of these parameters as a function of magnetic field for our sample have been interpreted. The obtained values of ß and γ, determined by analyzing the Arrott plots, are found to be T C = 298.66 ± 0.64 K, ß = 0.325 ± 0.001 and γ = 1.25 ± 0.01. The critical isotherm M (T C, µ 0 H) gives δ = 4.81 ± 0.01. These critical exponent values are found to be consistent and comparable to those predicted by the three-dimensional Ising model with short-range interaction. Thus, the Widom scaling law is fulfilled.

Correlation of crystal structure and optical properties of Ba0.97Nd0.0267Ti(1-x)W x O3 perovskite.

The Ba0.97Nd0.0267Ti(1-x)W x O3 (BNT x ) pervoskite with a single phase tetragonal structure was prepared at 900 °C using the Molten salt method. Raman spectra, Fourier transform infrared spectra (FT-IR), absorption spectra (Vis-NIR) and photoluminescence spectra (PL) in the temperature range from 10-300 K were used to investigate the correlations between the crystal structure and the optical properties of BNT x ceramics. Raman analyses and FT-IR indicated that the W6+ ions are incorporated sufficiently into into the BNT x lattice. The optical absorption spectra were recorded in the wavelength range of 400-1000 nm. The optical band gap (E g) and Urbach energy (E u) values were calculated from the absorption spectra. The emission spectra exhibited three prominent peaks located at 880, 1058 and 1340 nm corresponding to the 4F3/2 → 4I9/2,11/2,13/2 transition levels, respectively. They also showed a decrease in the intensity of emission spectra following the addition of W6+ ions. This decrease is due to the slight changes in the crystal environment around Nd3+ and the non-radiative energy transfer. According to the PL measurements, the study of power-excitation density confirmed that two photons at low energy are required to create the down-conversion (DC) emissions, implying that they may also have important applications as DC materials.

Theoretical investigations on the magnetocaloric and electrical properties of a perovskite manganite La(0.67)Ba(0.1)Ca(0.23)MnO3.

An investigation of the magnetic, magnetocaloric and electrical behavior of La(0.67)Ba(0.1)Ca(0.23)MnO3 is presented. The variation of magnetization (M) vs. temperature (T) under 1, 2, 3, 4 and 5 T magnetic fields reveals a ferromagnetic-paramagnetic transition. Magnetic entropy change, relative cooling power and specific heat for magnetic field variation were conducted using a phenomenological model. Moreover, the electrical resistivity is fitted with the phenomenological percolation model which is based on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. The equation of the form ΔS(P)(M)(T,H) = - α∫(H)(0)[∂(ln)(ρ)/∂(T)](H)(dH) relates the magnetic order to the transport behavior of our sample. The results show that the as obtained magnetic entropy change values are similar to those determined using data obtained from the investigation of the dependence of magnetization on the temperature and magnetic field.