NaF induced enhancement of luminous efficiency in narrow-band red-emitting K<Subscript>2</Subscript>TiF<Subscript>6</Subscript>:Mn<Superscript>4+</Superscript>@NaF phosphors

A series of K₂TiF₆:xMn⁴⁺ @NaF samples were prepared by the cation exchange method in HF solution. Coating effects of NaF on the fluorescent properties of the samples were discussed. It is interesting that NaF has induced enhancement of luminous efficiency for the samples. Mechanism of NaF induced enhanced luminescence effect was suggested. That is that the enhancement effect of NaF coating is mainly attributed to a suitable local distortion of the crystal field surrounding the Mn⁴⁺ activator through doping with NaF. The results indicate that the optimal conditions are x?=?0.07 and w_NaNO3?=?2.5 g. Decay lifetime and the photoluminescence quantum yield of the optimal sample are 5.25 ms and 99.19?±?0.03%, respectively. The chromaticity coordinates of the optimal sample are x?=?0.6926, y?=?0.3073. So, the phosphor emits deep red light, which can be applied for blue light-based white LED.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.     

Inducement of Itinerant Electron Transport in Charge-Ordered Pr<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> by Ba Doping

The effects of Ba ²⁺ doping on the electrical and magnetic properties of charge-ordered Pr_0.6Ca_0.4MnO₃ were investigated through electrical resistivity and AC susceptibility measurements. X-ray diffraction data analysis showed an increase in unit cell volume with increasing Ba ²⁺ content indicating the possibility of substituting Ba ²⁺ for the Ca-site. Electrical resistivity measurements showed insulating behavior and a resistivity anomaly at around 220 K. This anomaly is attributed to the existence of charge ordering transition temperature, \(T^{\mathrm {R}}_{\text {CO}}\) for the x = 0 sample. The Ba-substituted samples exhibited metallic to insulator transition (MI) behavior, with transition temperature, T _MI, increasing from ～98 K (x = 0.1) to ～122 K (x = 0.3). AC susceptibility measurements showed ferromagnetic to paramagnetic (FM-PM) transition for Ba-substituted samples with FM-PM transition temperature, T _c, increasing from ～121 K (x = 0.1) to ～170 K (x = 0.3), while for x = 0, an antiferromagnetic to paramagnetic transition behavior with transition temperature, T _N, ～170 K was observed. In addition, inverse susceptibility versus T plot showed a deviation from the Curie–Weiss behavior above T _c, indicating the existence of the Griffiths phase with deviation temperature, T _G, increasing from 160 K (x = 0.1) to 206 K (x = 0.3). Magnetoresistance, MR, behavior indicates intrinsic MR mechanism for x = 0.1 which changed to extrinsic MR for x > 0.2 as a result of Ba substitution. The weakening of charge ordering and inducement of ferromagnetic metallic (FMM) state as well as increase in both T _c and T _MI are suggested to be related to the increase of tolerance factor, τ, and increase of e _g ?electron bandwidth as average ionic radius at A-site, <r _A> increased with Ba substitution. The substitution may have reduced MnO₆ octahedral distortion and changed the Mn–O–Mn angle which, in turn, promotes itinerancy of charge carrier and enhanced double exchange mechanism. On the other hand, increase in A-site disorder, which is indicated by the increase in σ ² is suggested to be responsible for the widening of the difference between T _c and T _MI.     

Influence of Nd doping on microwave dielectric properties of SrTiO<Subscript>3</Subscript> ceramics

Sr_1?x Nd _x TiO₃ (x?=?0.08–0.14) ceramics were prepared by conventional solid-state methods. The analysis of crystal structure suggested Sr_1?x Nd _x TiO₃ ceramics appeared to form tetragonal perovskite structure. The relationship between charge compensation mechanism, microstructure feature and microwave dielectric properties were investigated. Trivalent Nd³⁺ substituting Sr²⁺ could effectively decrease oxygen vacancies. This reduction and relative density were critical to improve Q?×?f values of Sr_1?x Nd _x TiO₃ ceramics. For ε _r values, incorporation of Nd could restrain the rattling of Ti⁴⁺ cations and led to the reduction of dielectric constant. The τ _f values were strongly influenced by tilting of oxygen octahedral. The τ _f values decreased from 883 to 650 ppm/°C with x increasing from 0.08 to 0.14. A better microwave dielectric property was achieved for composition Sr_0.92Nd_0.08TiO₃ at 1460 °C: ε _r ?=?160, Q?×?f?=?6602 GHz, τ _f ?=?883 ppm/°C.     

The magnetic properties of BiY<Subscript>2</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles doped with Cr ions

BiY₂Cr _x Fe_5?x O₁₂ (x = 0, 0.05, 0.1, 0.2, 0.3) nanocrystals were synthesized by using a sol-gel method. Samples were characterized by the powder X-ray diffraction (XRD), the thermal gravity analysis (TGA) and the differential thermal analysis (DTA), the vibrating sample magnetometer(VSM) and Mössbauer spectrums. The average sizes of the particles were determined by the Scherrer’s formula. The special Ms and Mössbauer spectra of BiY₂Cr _x Fe_5?x O₁₂ nanocrystals are researched at room temperature. It is seen that the special Mss of samples are initially increased with increasing Cr³⁺ content (x < 0.1), and decreased with increasing content of Cr³⁺ ions (x > 0.1).     

Effect of Ni<Superscript>2+</Superscript> substitution on crystal structure and microwave dielectric properties for MgZrNb<Subscript>2</Subscript>O<Subscript>8</Subscript> ceramics

Monoclinic structured Mg_1?xNi_xZrNb₂O₈ (0?≤?x?≤?0.12) ceramics were synthesized for the first time through traditional solid-state reaction process and pure phase were obtained in all range. Rietveld refinement was used to analyze the crystal structure. With the increase of Ni²⁺ substitution amount, ε _r decreased, Q?×?f rose first then fell, τ _f shifted for the positive direction. Bond ionicity, lattice energy and bond energy were separately calculated to investigate the correlations with microwave dielectric properties. Typically, ceramics samples with the composition of Mg_0.92Ni_0.08ZrNb₂O₈ sintered at 1280 °C for 4 h exhibited the optimum microwave dielectric properties: ε _r ?=?24.58, Q?×?f?=?74534.1 GHz, τ _f ?=???49.11 ppm/°C, which could be a promising material for application.     

Phase relations in the Ag<Subscript>8</Subscript>SnS<Subscript>6</Subscript>-Ag<Subscript>2</Subscript>SnS<Subscript>3</Subscript>-AgBr system and crystal structure of Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript>

The T-x phase diagram of the Ag-Sn-S-Br system has been studied in the composition region Ag₈SnS₆-Ag₂SnS₃-AgBr, and a compound of composition Ag₆SnS₄Br₂ has been identified. Ag₆SnS₄Br₂ has a new structure, closely related to that of Ag₆GeS₄Br₂: sp. gr. Pnma, a = 6.67050(10), b = 7.82095(9), c = 23.1404(3) Å, Z = 4, R _B = 0.0519, R _wp = 0.0782, χ² = 1.36.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on the microstructure and electrical properties of LaMnO<Subscript>3</Subscript>-based NTC thermistors

A study to develop a new system of negative temperature coefficient thermistors for wide temperature range, A series of Mn-based perovskite-structured ceramics of composition (LaMn_1?x Al _x O₃)_0.9(Al₂O₃)_0.1 has been synthesized by conventional solid state reaction at 1350?°C. The X-ray diffraction patterns showed that for all the samples, the substitution of manganese by aluminum up to x?=?0.1 preserved the rhombohedral perovskite LaMnO₃-like phase. For x?=?0.2, apart from the LaMnO₃-like structure, a second perovskite phase based on the cubic LaAlO₃ structure was formed. For x?=?0.3 and 0.4, the phase present was LaAlO₃ -type structure. The grain sizes of the sintered body detected by scanning electron microscope were decreased with increasing Al₂O₃ content. The resistivity increases with increasing the Al content. The obtained values of ρ _25?°C and B _25/50 and E _a are in the range of 10–13103 Ω cm, 1813–2794 K, 0.156–0.241 eV, respectively. The resistance variation (ΔR/R) was <0.241% and the minimum value (0.0483%) was obtained for aging at 125?°C at 500 h. The aim of this work was explored new composite ceramics materials, which could be used as potential candidates for wide temperature range from ?100 to 500?°C thermistors applications.     

Effects of sintering temperature on the properties of Mn/Y codoped Ba<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>TiO<Subscript>3</Subscript> ceramics for tunable application

(Ba_0.67Sr_0.33)_1?3x/2Y _x Ti_1?y/2Mn _y O₃ [BST(Mn + Y), x = 0.006, y = 0.005] ceramics were fabricated by using citrate–nitrate combustion derived powder. Microstructure and dielectric properties of the BST(Mn + Y) ceramic samples were investigated within the sintering temperature ranged from 1220 to 1300 °C. Sintering temperature has a great influence on the microstructure and electrical properties of the ceramic samples. The dielectric properties, ferroelectric properties, and tunability are enhanced by optimizing sintering temperature. The relatively high tunability of 40 % (1.5 kV/mm DC field, 10 kHz) was obtained, and relatively low dielectric loss, <0.0052 (at 10 kHz, 20 °C) was acquired for BST(Mn + Y) samples sintered at 1275 °C for 3 h. Both the low dielectric loss and enhanced tunable properties of BST(Mn + Y) are useful for tunable devices application.     

Ultralow thermal conductivity of cerium-doped Nd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> over a wide doping range

In this paper, we report an ultralow thermal conductivity and a high-temperature phase stability of the (Nd_1?x Ce _x )₂Zr₂O_7+x system over the temperature range from room temperature to 1600 °C and over a wide composition range (0.2 ≤ x ≤ 0.8), and the (Nd_1?x Ce _x )₂Zr₂O_7+x system is therefore considered a strong candidate material for the fabrication of next-generation high-temperature thermal barrier coatings. The observed thermal conductivities (0.65–1.0 W/mK) are about 60–40% lower than those of undoped Nd₂Zr₂O₇ over the same temperature range (100–700 °C) and indicate a glass-like behavior. For comparison, the variation in the thermal conductivity with the temperature of the (Gd_1?x Ce _x )₂Zr₂O_7+x system with similar point defects was also measured, and the observed behavior was almost the same as that of undoped Gd₂Zr₂O₇ and was mostly determined by phonon–phonon scattering (λ ∝ 1/T). The effect of point defect scattering and strong phonon scattering sources (rattlers) on the thermal conductivity is also discussed in this paper. The results of this study suggest that the ultralow thermal conductivity of (Nd_1?x Ce _x )₂Zr₂O_7+x can be attributed to the presence of rattlers because of the large difference between the ionic radii of the Nd³⁺ and Ce⁴⁺ ions.     

Structural studies of a new electroceramic composite: Pb(Fe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> (PFN)-Cr<Subscript>0.75</Subscript>Fe<Subscript>1.25</Subscript>O<Subscript>3</Subscript>(CRFO)

A study of the structural characteristics of the composites [Pb(Fe_0.5Nb_0.5)O₃(PFN)] _x -[Cr_0.75Fe_1.25O₃(CRFO)]_100?x (x = 0 (CRFO100), 10, 50, 90, 100) was performed in this work. The compounds PFN100 and CRFO100 were prepared by conventional solid-state method and investigated by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and ⁵⁷Fe Mössbauer Spectroscopy techniques. The X-ray analysis shows that PFN100 is tetragonal and the CRFO100 phase has a trigonal symmetry. The refinement of all the composites was also performed and discussed in this paper. The Mössbauer spectrum for the composite samples shows a paramagnetic doublet and a sextet probably assigned to a magnetic phase associated to Fe⁺³. For the sample PFN100, only a magnetic field of 49.5 T (isomer shift (δ) = 0.21 mm/s) was detected. For the composite sample, the δ and Δ are typical of Fe ions at sites of octahedral coordination.     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

MOF-derived,CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-modified CoP/carbon composites for oxygen evolution and hydrogen evolution reactions

Development of low-cost, highly efficient catalysts for water splitting is required to replace precious metal catalysts. CeO _x -modified CoP@carbon composites are prepared via Ce-doped metal–organic frameworks. The as-prepared CeO _x -modified CoP@carbon composites have excellent electrocatalytic activity with respect to the oxygen evolution reaction, for which an overpotential (η) up to?~?313 mV is achieved at the current density of 10 mA cm^?2. In addition, CeO _x -modified CoP@carbon composites show an overpotential of up to 127 mV at the current density of 10 mA cm^?2 for the hydrogen evolution reaction, showing excellent catalytic activity for water splitting.     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.     

Effect of Al Substitution in Structural and Magnetic Properties of MnCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single-phase samples of Mn(Cr_1?x Al _x )₂O₄ (x = 0 – 0.30) with cubic spinel structure were prepared and the lattice constant is found to decrease from a = 8.4396 Å for x = 0 to a = 8.3801 Å for x = 0.30. The substitution of Al at Cr site is confirmed from the blue shift of Raman modes. Magnetization measurements and analysis show all the prepared samples exhibit ferrimagnetic transition with transition temperature in the range of 46 K for x = 0 to 33 K for x = 0.30. The saturation magnetization (M _s ) and the estimated anisotropy constant (K) show an anomalous behavior up to x = 0.10 and beyond that they decrease monotonously. They are explained by considering different site preferences of Al ³⁺ ions as the doping concentration is increased. The theoretical and experimental effective magnetic moment of the samples is found to be comparable and it decreases with increase in Al concentration.     

Magnetic and Electrical Properties Induced by the Substitution of Divalent by Monovalent in the La<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> Compound

The La_0.6Ca_0.4?x Ag _x MnO₃ samples with x = 0 and 0.10 were prepared by sol–gel methods. Structural and electrical measurements were performed to examine the effect of the silver substitution in the calcium sites on the physical properties. Magnetization versus temperature studies have shown that all samples exhibit a magnetic transition from ferromagnetic to paramagnetic phase when temperature is increased. The second transition in the resistivity in the La_0.6Ca_0.4MnO₃ compound can be attributed to an abnormality characteristic of charge ordering (CO) effect. The electrical resistivity was described by a phenomenological percolation model. Ten percent of Ag substitution in the Ca site exhibits a magnetoresistance value about 75 % near room temperature at the applied magnetic field of 8 T.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

Giant Magnetoresistance in Topological Insulator Bi<Subscript>1.98</Subscript>Nd<Subscript>0.02</Subscript>Se<Subscript>3</Subscript> Single Crystal

Doped topological insulators (TI) Bi_2?x Nd _x Se₃ single crystals were prepared by the self-flux method. The phase structure, magnetic properties, and electrical transport properties of the samples were studied. The X-ray diffraction (XRD) patterns of the sample indicate an incorporation of Nd into the Bi₂Se₃, and the crystal can be easily cleaved with silvery surface. The Bi_2?x Nd _x Se₃ sample shows a giant magnetoresistance (MR) with different magnetic field. The positive magnetoresistance (MR) can reach 190 % at the field of 9 Tesla when the field is perpendicular to ab-plane of the crystal. In addition, at low magnetic fields, the MR exhibits a weak antilocalization (WAL) cusp.     

New NaSrPO<Subscript>4</Subscript>:Sm<Superscript>3+</Superscript> phosphor as orange-red emitting material

Sm³⁺-activated NaSrPO₄ phosphors could be efficiently excited at 403 nm, and exhibited a bright red emission mainly including four wavelength peaks of 565, 600, 646 and 710 nm. The highest emission intensity was found for NaSr _1?x PO₄: xSm³⁺ with a composition of x = 0.007. Concentration quenching was observed as the composition of x exceeds 0.007. The decay time values of NaSr_1?x PO ₄ : xSm³⁺ phosphors range from around 2.55 to 3.49 ms. NaSr_1?x PO₄: xSm³⁺ phosphor shows a higher thermally stable luminescence and its thermal quenching temperature T ₅₀ was found to be 350°C, which is higher than that of commercial YAG:Ce³⁺ phosphor and ZnS:(Al, Ag) phosphor. Because NaSr_1?x PO₄: xSm³⁺ phosphor features a high colour-rendering index and chemical stability, it is potentially useful as a new scintillation material for white light-emitting diodes.