The giant dielectric tunability effect in bulk La2NiMnO6 around room temperature

The effect of applied dc bias electric field on dielectric permittivity in bulk La₂NiMnO₆ is investigated in this paper. It is found that a small bias field of 40 V/cm can greatly reduce the dielectric permittivity around the room temperature, compared to the much larger electric field that is required for conventional ferroelectric materials. The observed giant dielectric tunability is retained over a broad range of around room temperature and is most likely related to the charge ordering of Ni²⁺ and Mn⁴⁺ ions, further confirming the existence of electronic ferroelectricity in La₂NiMnO₆.     

The giant dielectric tunability effect in bulk Y<Subscript>2</Subscript>NiMnO<Subscript>6</Subscript> around room temperature

The effect of applied dc bias electric field on dielectric permittivity in bulk Y₂NiMnO₆ is investigated in this paper. It is found that a small bias field of 40 V/cm can greatly reduce the dielectric permittivity around the room temperature, compared to the much larger electric field that is required for conventional ferroelectric materials. The observed giant dielectric tunability is retained over a broad range of around room temperature and is most likely related to the charge ordering of Ni²⁺ and Mn⁴⁺ ions. This may further confirm the existence of electronic ferroelectricity in Y₂NiMnO₆.     

Effects of nickel doping on structural and optical properties of spinel lithium manganate thin films

Spinel LiNi_xMn_2−xO₄ (x≤0.9) thin films were synthesized by a sol-gel method employing spin-coating. The Ni-doped films were found to maintain cubic structure at low x but to exhibit a phase transition to tetragonal structure for x≥0.6. Such cubic-tetragonal phase transition can be explained in terms of Ni³⁺(d⁷) ions with low-spin (t_2g⁶,e_g¹) configuration occupying the octahedral sites of the compound, thus being subject to the Jahn-Teller effect. By X-ray photoelectron spectroscopy both Ni³⁺ and Ni²⁺ ions were detected where Ni²⁺ is more populated than Ni³⁺. Optical properties of the LiNi_xMn_2−xO₄ films were investigated by spectroscopic ellipsometry in the visible-ultraviolet range. The measured dielectric function spectra mainly consist of broad absorption structures attributed to charge-transfer transitions, O²⁻(2p)→Mn⁴⁺(3d) for 1.9 (t_2g) and 2.8-3.0 eV (e_g) structures and O²⁻(2p)→Mn³⁺(3d) for 2.3 (t_2g) and 3.4-3.6 eV (e_g) structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as being due to d-d crystal-field transitions within the octahedral Mn³⁺ ion. In terms of these transitions, the evolution of the optical absorption spectrum of LiMn₂O₄ by Ni doping could be explained and the related electronic structure parameters were obtained.     

Luminescent properties of La2LiTaO6:Mn4+ and its application as red emission LEDs phosphor

A novel phosphor, Mn⁴⁺ doped La₂LiTaO₆, was developed by solid-state reaction method. The luminescent spectra and emission efficiencies of La₂LiTaO₆:Mn _x ⁴⁺ (x = 0.001, 0.003, 0.005 and 0.01) were discussed. The effects of co-doped charge compensation ions, M = Mg²⁺, Ca²⁺, Na⁺, were investigated, respectively. The excitation spectra indicated that La₂LiTaO₆:Mn⁴⁺ could be effectively excited by both NUV light and blue light. The emission spectra of the phosphor exhibit a broadband ranging from 670 to 720 nm with the maximum at about 709 nm in deep red region. The co-doping of Mg²⁺ could significantly improve the luminescent properties of La₂LiTaO₆:Mn⁴⁺. Thus, phosphor La₂LiTaO₆:Mn⁴⁺, Mg²⁺ can serve as a key component to improve color rendering of blue-chip white-LEDs.     

Valence state of manganese ions in the La1−α BiLaβMnLa1−δ OLa3±γ ceramics

The valence state of the Mn ions in ceramic samples of the La_1?α BiLa_βMnLa_1?δ OLa_3±γ composition (LBMO) has been studied using the X-ray photoelectron spectroscopy. The presence of Mn³⁺ and Mn⁴⁺ ions in these compounds has been shown. The relative content Mn³⁺/Mn⁴⁺ has been determined by means of fitting the experimental Mn 2p spectra by the superposition of theoretical spectra of Mn³⁺ and Mn⁴⁺ ions. The elemental composition of the samples has been determined by the X-ray photoelectron spectroscopy and electron probe microanalysis. It has been established that the relative content of Mn⁴⁺ ions correlates with parameter δ, which characterizes the deviation of the actual elemental composition of the La_1?α BiLa_βMnLa_1?δ OLa_3±γ ceramics from stoichiometry La_{1 ? x} Bi _x MnO₃.     

Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

About the nature of Ni3+ magnetic centres in the LaSrAl1−xNixO4 ceramics

LaSrAl_1?x Ni _x 0₄ (x≤0.11) ceramics werer studied by EPR. It was established that Ni³⁺ ions in this compound may be in two states: a low spin one with t _2g ⁶ e _g ¹ electron configuration and high spin state with t _2g ⁵ e _g ² electron configuration. It was shown that the random distribution of La³⁺ and Sr²⁺ ions in the heavy metal sublattice leads to two kinds for each type of these centres with different degree of tetragonal distortions. The total concentration of NiO₆ isolated centres in these ceramics does not exceed 5–10 % of a total number of nickel ions at a givenx. A model, explaining these peculiarities observed in an experiment by the enhanced tendency of Ni³⁺ ions to clusterization, was proposed. It appears that even at small concentrations Ni³⁺ ions form clusters and conglomerates, whose structural characteristics of the oxygen octahedra are comparable with those in LaSrNiO₄.     

Imperfection of the clustered perovskite structure, phase transitions, and magnetoresistive properties of ceramic La0.6Sr0.2Mn1.2 ? x Ni x O3 ± δ (x = 0–0.3)

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Ni _x O_{3 ± ??} (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??_ac), ⁵⁵Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn²⁺ ions in the A-positions. The substitution of Ni³⁺ ions (r = 0.74 ?) for Mn³⁺ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T _C, and the metal-semiconductor phase transition temperature T _ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn³⁺ and Mn⁴⁺. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn²⁺ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn³⁺ ? O^2? ? Mn⁴⁺; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn⁴⁺ ions. The local hyperfine interaction fields on ⁵⁵Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn³⁺ ? O^2? ? Mn⁴⁺. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.     

Tuning the magnetocaloric properties of La0.7Ca0.3MnO3 manganites through Ni-doping

The effect of Ni²⁺ doping on the magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ manganites synthesized via the auto-combustion method is reported. The aim of studying Ni²⁺-substituted La_0.7Ca_0.3Mn_1 ? xNi_xO₃ ($x=0,0.02,0.07$, and 0.1) manganites was to explore the possibility of increasing the operating temperature range for the magnetocaloric effect through tuning of the magnetic transition temperature. X-ray diffraction analysis confirmed the phase purity of the synthesized samples. The substitution of Mn³⁺ ions by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice was also corroborated through this technique. The dependence of the magnetization on the temperature reveals that all the compositions exhibit a well-defined ferromagnetic to paramagnetic transition near the Curie temperature. A systematic decrease in the values of the Curie temperature is clearly observed upon Ni²⁺ doping. Probably the replacement of Mn³⁺ by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice weakens the Mn³⁺–O–Mn⁴⁺ double exchange interaction, which leads to a decrease in the transition temperature and the magnetic moment in the samples. By using Arrott plots, it was found that the phase transition from ferromagnetic to paramagnetic is second order. The maximum magnetic entropy changes observed for the $x=0,0.02,0.07$, and 0.1 composites was 0.85, 0.77, 0.63, and 0.59 J/kg?K, respectively, under a magnetic field of 1.5 T. In general, it was verified that the magnetic entropy change achieved for La_0.7Ca_0.3Mn_1 ? xNi_xO₃ manganites synthesized via the auto-combustion method is higher than those reported for other manganites with comparable Ni²⁺-doping levels synthesized via standard solid state reaction. The addition of Ni²⁺ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (～60 J/kg) is found for a Ni-doping level of 2% around 230 K in a field of 1.5 T.     

Etude par diffraction neutronique de l'ilmenite ferrimagnetique NiMnO3

The magnetic structure of ferrimagnetic ilmenite Ni²⁺Mn⁴⁺O₃ has been investigated by neutron diffraction. Below the Curie temperature (164°C), the spins are oriented into two kinds of ferromagnetic planes perpendicular to the [111] rhomboedral axis, one containing Mn⁴⁺ and the other Ni²⁺ cation. Two successive planes are coupled antiferromagnetically. The experimental magnetic moments are respectively found equal to 1.8 and 2.2 μ_B for Ni²⁺ and Mn⁴⁺ at room temperature. The positional atomic parameters have been redetermined from nuclear diffraction data taken above the Curie temperature.     

Comparison of piezoelectricity in Ta and La substituted lead calcium titanate ceramics

This paper reports the experimental investigations on the effect of La³⁺ and Ta⁵⁺ substitution on the structural characteristics and dielectric and piezoelectric properties of lead calcium titanate (PCT) ceramic. The PCT samples with A-site and B-site substitution having the composition formula Pb_0.76−x/2La_xCa_0.24(Ti_0.98Mn_0.02)_1−x/2O₃ and Pb_0.76Ca_0.24Mn_0.02Ti _0.98−5x/4Ta_xO₃, x=0 and 0.02, respectively_, were prepared using conventional solid-state reaction method. Phase formation and structural analysis were studied using X-ray diffraction and scanning electron microscopy, respectively. Dielectric constant (ε′) and loss tangent (tan δ) as a function of frequency were measured at room temperature as well as elevated temperature. Both ε′ and tan δ decreased with increase in frequency at room temperature. Curie temperature decreased with La and Ta doping in PCT ceramics due to a decrease in the tetragonality of PCT ceramics. Piezoelectric charge coefficients (d₃₃, d₃₁) increased with La³⁺ substitution due to reorientation of the grains and decreased with Ta⁵⁺ substitution because of the increase in porosity. Figure of merit d_hg_h increased and decreased with La and Ta substitution, respectively. A good ferroelectric behaviour is obtained for La substitution, while no hysteresis is obtained for Ta substitution.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Room temperature magnetoresistance in Ln2/3A1/3MnO3 manganites

The investigation of the manganites La_2/3−xPr_xSr_1/3MnO₃, La_2/3Sr_1/3−xCa_xMnO₃ and La_2/3+xCa_1/3−2xAg_xMnO₃, which all exhibit Mn³⁺:Mn⁴⁺=2, shows that it is possible to reach high magnetoresistance at room temperature, up to 21% under 1.2 T. These materials are compared to La_5/6Ag_1/6MnO₃ which corresponds to the same Mn³⁺:Mn⁴⁺ ratio and exhibits a magnetoresistance of 25% in this field. An interesting feature deals with the value of the insulator-metal transition temperature T_IM, often higher than T_C, especially for Ag-based compounds. It is suggested that the latter results either from a better oxygenation of the surface of the grains or from a migration of silver toward the surface.     

La substitution in four-layers Aurivillius phase SrBi4Ti4O15

Ceramics with the nominal composition of SrBi_4−xLa_xTi₄O₁₅ have been prepared within the range of 0≤x≤1.8, and the dielectric properties are investigated. Single phase SrBi_4−xLa_xTi₄O₁₅ solid solution exists until the secondary phase of La_2/3TiO₃ appears at x=1.6. The Curie temperature is 520 °C for pure SrBi₄Ti₄O₁₅, and it shifts to low temperature with increasing x, which is due to the smaller structural distortion caused by La³⁺ substitution. In addition, the dielectric constant anomaly is suppressed with the substitution. No dielectric relaxation behavior is observed. When x≥1.2, the paraelectric state is attained in the present ceramics. La³⁺ substitution effects on the SrBi₄Ti₄O₁₅ ceramics are also compared with the previous work on Bi_4−xLa_xTi₃O₁₂.     

Electrochemical reaction of 5 V cathode LiNi0.4Mn1.6O4

LiNi_0.4Mn_1.6O₄ was prepared under air and oxygen atmospheres using fine Mn₃O₄ particle and large MnO₂ particle at various temperatures. The sample prepared from Mn₃O₄ at 750 °C under air or oxygen atmosphere exhibited an ideal electrochemical behavior, which was based on three redox couples of Mn³⁺/Mn⁴⁺, Ni²⁺/Ni³⁺, and Ni³⁺/Ni⁴⁺. On the other hand, the sample prepared from MnO₂ had a larger capacity at 4 V plateau and smaller one at 5 V plateau. However, when using oxygen atmosphere, the sample exhibited more ideal behavior, which is similar to the sample prepared from Mn₃O₄. This means that some defects exist in LiNi_0.4Mn_1.6O₄, depending on preparation conditions. In order to confirm this point, the chemical composition and the valence state of Mn of the prepared sample was analyzed. From these results, it can be said that electrochemical reactions of LiNi_0.4Mn_1.6O₄ are well explained based on three redox couples of Mn³⁺/Mn⁴⁺, Ni²⁺/Ni³⁺, and Ni³⁺/Ni⁴⁺ by considering a presence of oxygen defects.     

Synthesis and characterization of layered perovskite oxides La1 + x Sr2 − x MnCrO7 (x = 0.2, 0.5)

Intergrowth perovskite type complex oxides of composition La_1.2Sr_1.8MnCrO₇ and La_1.5Sr_1.5MnCrO₇ have been synthesized by ceramic method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. Both the phases behave as insulators in the high temperature region and the linearity of log ρ versus T ^?1/4 plot in the temperature range 150–300 K shows that the electronic conduction occurs by a 3D variable range hopping mechanism. The phases show insulator-metal transition at low temperature which could be due to the mixed valence state of Mn³⁺/Mn⁴⁺ by double exchange mechanism. The ferromagnetic interactions observed for the samples arises from double exchange interaction between Mn ³⁺ and Mn⁴⁺ and Cr³⁺ and Mn³⁺ ions.     

Structural and magnetic heterogeneities, phase transitions, 55Mn NMR, and magnetoresistive properties of La0.6Sr0.3 − x Bi x Mn1.1O3

The structural, resistive, magnetic, and magnetoresistive properties of the La_0.6Sr_{0.3 ? x} Bi _x Mn_1.1O₃ ceramics have been studied. The substitution of Bi ions for Sr ions increases the lattice parameter of the rhombohedral perovskite structure, decreases the metal-semiconductor and ferromagnet-paramagnet phase transition temperatures and the peak of the magnetoresistive effect, and increases the resistivity, approaching the system to the ferroelectric state. The ⁵⁵Mn NVR study indicates on the high-frequency Mn³⁺ ? Mn⁴⁺ superexchange and heterogeneity of the valence and magnetic states of manganese due to the nonuniformity of distribution of all ions and defects. The phase diagram has been constructed, which shows a strong correlation between the structural, magnetic, and magnetoresistive properties.     

Origin of the electron spin resonance signal in the manganites: from polarons to phase separation

In the manganites L_1?xM_xMnO₃ (L = La, Nd, Pr, …; M = Sr, Ba, Ca, …), the doping concentration introduces a mixed valence (Mn³⁺, Mn⁴⁺) which governs the magnetic and electric properties of the compound. Mn³⁺ (S = 2) is scarcely observed in electron spin resonance (ESR). In contrast, Mn⁴⁺ (S = 3/2), is a good ESR probe. However, X-band measurements show an enhanced Mn⁴⁺ susceptibility, which is the signature of some kind of coupling of the Mn⁴⁺ ions with the Mn³⁺ ions, but its exact nature is still controversial. We present multifrequency ESR experiments (9–385 GHz) obtained on different systems (La_1?δMnO₃, La_1?xMnO₃, La_1?xCa_xMnO₃, and Nd_1?xCa_xMnO₃) in the low-concentration range (0 <x< 0.33). In the paramagnetic regime, the Mn³⁺ spectrum cannot be observed because of fast relaxation. The signal arises from polarons, whose size, temperature and magnetic field dependences vary with M andx. The single line observed in the metallic compound evolves towards a double-peak structure visible at high frequency in La_0.97MnO₃. Its evolution with temperature below the magnetic transition reveals the presence of manganese ions in a different magnetic environment, i.e., phase separation. The magnetic order of the separated phase is not ferromagnetic. It is a more complex order, which depends substantially on the nature of the cation M.