High-density sol-gel derived,cold-isostatically pressed La0.67Ca0.27Sr0.06MnO3 polycrystalline ceramics and their room-temperature TCR improvement

In this study, high-density La_0.67Ca_0.27Sr_0.06MnO₃ (LCSMO) ceramics were successfully obtained by sol-gel method followed by cold isostatic pressing (CIP) under 250 MPa. Effects of sintering temperature (T_S, 1250 °C ≤ T_S ≤ 1450 °C) on structure, surface chemical, electrical, and optical properties of as-obtained LCSMO ceramics were investigated by X-ray diffraction (XRD, BDX3200), X-ray photoemission spectroscopy (XPS, Thermo Fisher Scientific), a four-probe system (East changing ET9005), Fourier transform infrared spectrometry (FTIR, TENSOR 27), Raman microscopy (RENISHAW inVia) and UV–vis spectrophotometry (HITACHI U-4100), respectively. All prepared samples showed orthorhombic structure with Pnma space group. As T_S increased, grain size gradually rose from 2.71 to 7.30 μm. XRD refinement, Raman, and FTIR all depicted constant of bond angle and length of Mn–O. Hence, variation in T_S did not cause lattice distortion inside samples. The best electrical properties were obtained at 1450 °C, where resistivity (ρ) fell below 0.008 Ω cm and temperature coefficient of resistivity (TCR) reached 13.0% K^?1 at 289.2 K (room temperature).It is worth noting that electrical performance was indeed improved due to high densities of samples under processing of CIP. Overall, the change in T_S from 1250 to 1450 °C greatly influenced electrical behaviors but showed little effect on structural and optical properties of LCSMO ceramics.     

Magnetic properties of La0.7Sr0.3MnO3 under the pressure and the transport property under the magnetic field

Polycrystalline La_0.7Sr_0.3MnO₃ sample (LSMO) was synthesized by the solid phase reaction; it exhibits the paramagnetic-ferromagnetic transition at T_c = 362 K at the ambient pressure; it is paramagnetic metallic state above T_c and the ferromagnetic metallic state below T_c. It was observed that the pressure effect depends on the temperature range: (a) In the paramagnetic region, the magnetization M hardly changes with the pressure P, that is, ΔM≈0. There exist the antiferromagnetic (AFM) coupled ferromagnetic clusters in the paramagnetic region, and the pressure enhances the AFM coupling. (b) In the temperature range around T_c, the pressure increases M, that is, ΔM > 0, with the concomitant increase in T_c; the average pressure coefficient dT_c/dP is 5.40 K/GPa at P = .74 GPa, much smaller than 15.47 and 15.90 K/GPa for La_0.7Ca_0.3MnO₃ and La_0.9Ca_0.1MnO₃, respectively, due to the different distortion degree of MnO₆ octahedra in Ca and Sr doped manganites. (c) In the temperature region below T_c, the pressure reduces M, that is, ΔM < 0. M is determined by the competition between the Mn³⁺-O-Mn⁴⁺ double exchange and the interparticle dipolar interaction. The pressure enhances the interparticle dipolar interaction, leading to a significant decrease in magnetization. The resistivity of LSMO exhibits the metallic behavior in the temperature range of 5 K~370 K; it decreases as the applied magnetic field H increases from 0 to 7 T, that is, the magnetoresistance effect which is more significant around T_c. The fitting to the low-temperature resistivity shows that the applied magnetic field reduces the scattering from the grain boundary, electron, phonon, and magnon, especially reduces the electron-electron scattering.     

La0.7-xDyxSr0.3MnO3体系低温磁行为和电阻率的反常

通过测量样品的磁化强度-温度(M-T)曲线、电阻率-温度(ρ-T)曲线及磁电阻-温度(MR-T)曲线．研究了Dy掺杂(0．00≤x≤0．30)对La0．7-xDyxSr0．3MnO3体系磁电性质的影响。实验发现：随Dy掺杂量的增加,体系的磁结构从长程铁磁有序向自旋团簇玻璃态、反铁磁状态转变。x为0．20．0．30时的低温磁行为发生异常,电行为存在低温电阻率极小值的现象。这些现象不仅来源于掺杂引起的晶格效应．而且来源于掺杂引起的额外磁性耦合。     

A-site Ca/Sr co-doping to optimize room-temperature TCR of La0.7Ca0.3-xSrxMnO3 films

Based on the analysis of crystal structure, Mn³⁺/Mn⁴⁺ pairs, distortion of MnO₆ octahedron, and electrical transport properties of La_1-xCa_xMnO₃ and La_1-xSr_xMnO₃ materials, room-temperature coefficient of resistivity (TCR) of La_0.7Ca_0.3-xSr_xMnO₃ (LCSMO) films was optimized by Ca/Sr co-doping at the A-site. LCSMO films are successfully fabricated on LaAlO₃ (100) substrates via facile spin coating technology. The microstructure of LCSMO films is characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy and X-ray photoemission spectroscopy. Results reveal that A-site Ca/Sr co-doping significantly influenced crystal structure, formation of Mn³⁺/Mn⁴⁺ pairs, and distortion of MnO₆ octahedron. The correlation between microstructure and electrical transport properties was explained through the phenomenological percolation model, double-exchange mechanism and Jahn-Teller effect. Furthermore, the TCR reached 10.2% K^-1 at 296.1 K in La_0.7Ca_0.18Sr_0.12MnO₃ films.     

Effect of La substitution on energy storage properties of (Bi0.2Na0.2Ca0.2Ba0.2Sr0.2)TiO3 lead-free high-entropy ceramics

In this study, a novel lead-free high-entropy ceramic (HEC) system, (Bi_0.2Na_0.2Ca_0.2Ba_0.2Sr_0.2)_(1–3x/2)La_xTiO₃ (0 ≤ x ≤ 0.15) (abbreviated as BNCBST-xLa), was designed to enhance energy storage performance through La substitution and prepared via a hydrothermal method. Results indicate that La doping at A site in BNCBST induces lattice distortion and further improves dielectric relaxation. Moreover, grain growth is inhibited by the La content, which results in an increase in the insulation resistance and thus significant enhancement in the electric breakdown strength (E_b). Accordingly, the system with x = 0.03 exhibits an excellent recoverable energy density (W_rec) of 2.43 J/cm³ and a high energy storage efficiency (η) of 85.5% under a great E_b of 245 kV/cm, together with wide temperature stability (W_rec and η vary within ± 8.3% and ± 1.1% at 30–150°C). The findings of this study suggest that the obtained La-modified BNBCST HECs are promising for energy storage applications.     

Co-optimization of Na and K doping for improved room-temperature TCR of La0.7(Na0.3-xKx)MnO3 polycrystalline ceramics

Polycrystalline La_0.7(Na_0.3-xK_x)MnO₃ (LNKMO, x = 0.10, 0.15, 0.20, 0.25, and 0.26) ceramics were successfully compounded by adopting conventional sol-gel technology. The physical properties of as-prepared specimens were closely related to their morphology and internal structure, which were characterized and analyzed via X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy. Results confirmed that La⁺ ions located at A-sites in crystal lattice were partially substituted by doped Na⁺ and K⁺ ions, which resulted in rotation and distortion of MnO₆ octahedron. Lattice distortion was primary factor behind double exchange (DE) mechanism and Jahn-Teller (JT) effects. In addition, Na and K dopants altered relative amount of Mn³⁺ and Mn⁴⁺ ions, causing intensity variation in DE effect. These changes contributed to a decline in resistivity and an increase in peak resistance temperature (T_k) with increasing K doping level. Meanwhile, optimal temperature coefficient of resistance (TCR) value of LNKMO ceramics reached 8.48% K^?1 at 292.14 K when x = 0.25. This work reveals the mechanism of Na and K co-doping to optimize electrical transport properties of LNKMO manganese oxides and provides excellent material for the fabrication of uncooled infrared bolometers.     

Robust temperature coefficient of resistance of polycrystalline La0.6Ca0.4MnO3 under magnetic fields at room temperature

In the presence of magnetic field, reducing the loss in temperature coefficient of resistance (TCR) and increasing metal−insulator transition point (T_MI) to room temperature are the most important concerns for the application of perovskite manganites in high−precision thermistors. Based on emerging evidence, relevant factor to address these problems lies in the interaction between Jahn−Teller (JT) distortion and magnetic field, which results in spin−orbital coupling (SOC) effect and significantly influences TCR and T_MI. In this work, we studied the magnetic field induced SOC effect in polycrystalline La_1−xCa_xMnO₃ (x = 0.225–0.45) materials synthesized via sol−gel technique. Compounds undergo the JT distortions with increasing Ca dopant content, and the most pronounced distortion of 0.0144 at x = 0.40 is correlated with a basal−plane distortion mode. All samples exhibit T_MI values between 262 K and 288 K, indicating the enhancement of doping−induced double−exchange interaction. In the magnetic field of 1 T, SOC effect sufficiently suppresses the deterioration of TCR caused by deficient magnetization in La_0.6Ca_0.4MnO₃ to a value of 2.9%·K⁻¹ at room temperature (287 K).     

Significantly enhanced room-temperature TCR and MR of La0.67K0.33-xSrxMnO3 ceramics by adjusting Sr content

Strontium (Sr)-doped La_0.67K_0.33-xSr_xMnO₃ (LKSMO) ceramics were obtained by traditional sol-gel method. With increasing Sr content, full width at half maximum (FWHM) for temperature-dependent resistivity curves increased, resistivity decreased, and peak resistivity temperature (T_P) shifted toward high temperature. Microstructure of LKSMO ceramics was characterized by X-ray diffraction, scanning electron microscopy, X-ray photoemission spectroscopy, energy dispersive spectrometry, and Fourier transform infrared spectroscopy, etc. Connection between microstructure and properties of ceramics was studied by combining double exchange mechanism, Jahn-Teller effect, and phenomenological percolation model. Electrical transport mechanism of ferromagnetic metal (FMM) and paramagnetic insulator (PMI) regions was employed to explain temperature coefficient of resistivity (TCR) and magnetoresistance (MR) behaviors of as-obtained samples. Various scattering factors, effective mass of itinerant electron, and energy difference between FMM and PMI phases affected FWHM of ρ-T curves in Sr-doped LKSMO ceramics. In sum, these findings provide physical mechanism and experimental guidance for synthesis of high-TCR and MR polycrystalline ceramics at room temperature.     

Enhancement of grain growth and electrical conductivity of La0.8Sr0.2MnO3 ceramics by microwave irradiation

We studied crystallization, grain growth and electric properties of La_0.8Sr_0.2MnO₃ (LSM) ceramics which were produced using the microwave-treatment. While co-precipitated nanoparticles remain mainly amorphous, the microwave irradiated particles are crystallized into LSM and La₂Mn₂O₇ at 550 °C, due to higher dielectric polarizability of La. This, in turn, decreases the amount of the second phase La₂O₃ in calcined powder and promotes the growth of perovskite grains during sintering at 1400 °C. Larger grains of LSM ceramics lower the activation energy of small polaron hopping from 0.35 eV to 0.24 eV and increases high-temperature electric conductivity. In addition, high crystallinity of LSM ceramics from the microwave-treatment suppresses a chemical reaction with ZrO₂ and NiO in a temperature range of 900 – 1100 °C under oxidizing and reducing ambiances. These results show that LSM ceramics from the microwave-assisted reaction meet requirements for an interconnect layer for solid oxide electrolysis cells.     

High energy storage density and efficiency in nanostructured (Bi0.2Na0.2K0.2La0.2Sr0.2)TiO3 high-entropy ceramics

High-entropy ceramics (HECs) (Bi_0.2Na_0.2K_0.2La_0.2Sr_0.2)TiO₃ (BNKLST) with single-phase perovskite structure have been successfully prepared by a modified citrate acid method. In comparison to (Bi_0.5Na_0.5)TiO₃ (BNT) ceramics prepared by the same synthesis route, the BNKLST HECs exhibit dense nanostructures with grain sizes as small as 45 nm, which are suggested to be responsible for the significantly improved electric breakdown fields and reduced leakage currents in the ceramics, and they have much enhanced elastic modulus owing to the entropy-stabilized perovskite structure. The electrical and dielectric characterizations reveal that BNKLST has high electrical resistances and dielectric constants at elevated temperatures, and, in particular, a recoverable energy storage density of 0.959 J/cm³ can be achieved under an applied electric field of 180 kV/cm. Moreover, the energy storage efficiency in BNKLST can be maintained to be larger than 90% at 40–200°C. These excellent properties suggest that entropy-stabilized BNT-based ceramics are promising dielectrics for electrical energy storage applications.     

Structural,morphological, and magnetic properties of sol-gel derived La0.7Ca0.3MnO3 manganite nanoparticles

La_0.7Ca_0.3MnO₃ (LCMO) manganite nanoparticles are synthesized via a sol-gel route at different annealed temperatures. Their structural, morphological, and magnetic properties are investigated. The X-ray diffraction patterns coupled with electron diffraction confirm that all the LCMO samples are single phase and crystallize in the orthorhombic perovskite structure (Pnma space group). The morphology of the samples observed by TEM, reveals a spherical shape with an average grain size lower than 50 nm. The resolved lattice fringes in high-resolution TEM images also reveal the single crystalline nature of the LCMO nanoparticles. Magnetization measurements versus temperature under low magnetic field (0.01 T) show a paramagnetic - ferromagnetic transition for all the samples. The Curie temperature (T_c) is found to be decreased with increasing the annealed temperature. A bifurcation is observed in the zero field-cooled and field-cooled magnetizations, indicating a competition between ferromagnetic and antiferromagnetic interactions in the nanoparticles at low temperatures. Field-cooled hysteresis measurements suggest a cluster glasslike behavior of the nanoparticles. Room temperature and low temperature M - H loops demonstrate that all the samples exhibit ferromagnetic behavior at 5 K, whereas a paramagnetic behavior at room temperature. Resistivity behavior of the LCMO samples shows that they exhibit a metal - insulator transition. Magnetoresistance of ~ 50% at the field up to 8 T was observed at 2 K in the LSCO samples annealed at 600 °C.     

Structural characterization and magnetic properties of single-crystalline (La0.6Pr0.4)0.67Ca0.33MnO3 nanowires

Herein, structural and magnetic properties of single-crystalline (La_0.6Pr_0.4)_0.67Ca_0.33MnO₃ nanowires synthesized via a hydrothermal process are reported. The nanowires are crystallized in an orthorhombic structure (Pnma space group). Their lattice parameters follow the relationship a ≈ c ≈ b/√2 These nanowires exhibited a clean and smooth surface with diameters of 60-120 nm and an average length of approximately 2.0 μm. High-resolution transmission electron microscopy images confirmed the single-crystalline nature of the nanowires growing along the [100] direction. The nanowires demonstrated magnetic hysteresis loops at low temperatures and a weak exchange bias (EB) effect. Paramagnetic (PM)–ferromagnetic (FM) phase transition occurred at a Curie temperature (T_C) of 224 K, and strong irreversibility between zero-field-cooled (ZFC) and field-cooled (FC) magnetization (M_ZFC and M_FC, respectively) curves was observed at 273 K. The M_ZFC curve exhibited a significantly broad peak with a maximum at a freezing temperature (T_f) of 134 K. Relative difference between M_FC and M_ZFC in the nanowires [(M_FC − M_ZFC)/M_FC] rapidly increased below T_f and reached approximately 50% below 35 K. The effective magnetic moment deduced from the Curie constant is larger than the theoretical value, indicating short-range FM interactions in the nanowires. A positive PM T_C (θ_p) implies dominant FM interactions in the nanowires, and θ_p > T_C observed herein indicates the existence of short-range ordered states above T_C.     

Improvement of electrical and magnetic properties in La0.67Ca0.33Mn0.97Co0.03O3 ceramic by Ag doping

For the perovskite manganite La_1-xCa_xMnO₃, achieving high temperature coefficient of resistance (TCR) and magnetoresistance (MR) is the key to realize its potential applications. In this study, high-quality La_0.67Ca_0.33Mn_0.97Co_0.03O₃:Ag_x polycrystalline ceramics were prepared by the sol-gel method. The results show that Ag doping has important impact on metal-insulator and ferromagnetic-paramagnetic transitions. A Ag doping amount increases, the grain size of the samples increases at x = 0.05 and then decreases. The doping of Ag can improve the crystalline quality of the samples and enhance the connectivity between grains, thereby improving the metallicity of the system. Additionally, with Ag doping amount increases, the resistivity of the samples gradually decreased, while the Curie temperature and the metal-insulator transition temperature gradually increased. Especially after Ag doping, both the TCR peak (TCR_peak) and the MR peak (MR_peak) values are significantly improved. The TCR_peak reaches 65.2%·K^?1 at x = 0.1, while the MR_peak is as high as 82.6% at x = 0.05 under 1 T magnetic field. Doping perovskite manganite ceramics with Co and Ag can greatly optimize their TCR and MR, favoring the potential applications of these materials.     

Effect of different post-annealing durations on electromagnetic properties of La0.67Ca0.33MnO3:Ag0.2 thin films prepared by pulsed laser deposition

La_0.67Ca_0.33MnO₃:Ag_0.2 thin films were obtained by pulsed laser deposition followed by post-annealing at 1200 °C for varied durations. Surface morphologies, structures, and electrical and magnetic properties of films prepared with different annealing durations were significantly different. X-ray diffraction results showed that annealed films exhibited stronger diffraction peaks and C-axis preferred growth. Regarding their electrical properties, metal-insulator transition temperature (T_MI) and temperature coefficient of resistance (TCR) increased first and then decreased with the increase in annealing duration. In terms of their magnetic properties, thin films displayed ferromagnetic-paramagnetic transition. With the increase in annealing duration, Curie temperature increased first and then decreased. Specifically, the film annealed for 3 h showed excellent electromagnetic properties, with relatively high TCR of 20.3%·K^-1 and near room temperature T_MI of 285.7 °C. Owing to these excellent properties, as-prepared thin films have application potential in infrared detectors.     

Novel high-entropy microwave dielectric ceramics Sr(La0.2Nd0.2Sm0.2Eu0.2Gd0.2)AlO4 with excellent temperature stability and mechanical properties

Novel high-entropy Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics with a layered perovskite structure have been prepared via the standard solid-state reaction method. The design of high-entropy improves the bond valence and subsequently optimizes the large negative temperature coefficient of resonant frequency (τ_f = ?32 ppm/°C) of the simple SrLaAlO₄ ceramics. Excellent temperature stability (τ_f = ?6 ppm/°C) together with a relative permittivity (ε_r) of 18.6 and a quality factor (Qf = 14,509 GHz) are obtained in Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics sintered at 1475 °C. It indicates that the present ceramics have great application prospects in passive microwave components such as resonators and filters. Meanwhile, significant improvements in compressive strength and strain are achieved, which are 1040 MPa and 15.7% for Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ compared to 583 MPa and 12% in SrLaAlO₄. The enhanced mechanical properties originate from the dislocation strengthening mechanism as the intertwining of interlayer lattices is revealed from the high-resolution transmission electronic micrographs.