Effect of the Mn ion on electrical and magnetic properties of orthorhombic perovskite-type Ca(Mn1−xTix)O3−δ

Orthorhombic perovskite-type Ca(Mn_1−xTi_x)O_3−δ (0 ≤ x ≤ 0.7) was synthesized at 1173 K for 12 h in a flow of oxygen from a precursor gel prepared using citric acid and ethylene glycol. The Mn³⁺ ion was generated by substituting a Ti⁴⁺ ion in CaMnO₃. The average particle size was 100-300 nm and did not depend on x. The lattice constants and the (Mn, Ti)-O distance increased linearly with increasing x. The variation in global instability index (GII) indicated that the instability of the structure increases monotonically with increasing x. Ca(Mn_1−xTi_x)O_3−δ was an n-type semiconductor that had its minimum values of electrical resistivity (ρ) and activation energy (E_a) at x = 0.1. Ca(Mn_1−xTi_x)O_3−δ (x = 0 and 0.1) exhibited a weak ferromagnetic behavior. The variation in μ_eff indicated that the spin state of the Mn³⁺ ion changes from low to high at x = 0.1, then reverts to low in the range of 0.2 ≤ x ≤ 0.7. The variations in ρ and E_a are explained by the number of electrons according to the change in the spin state of the Mn³⁺ ion.     

Electrochemical behaviors of Li[Li(1−x)/3Mn(2−x)/3Nix/3Cox/3]O2 cathode series (0 < x < 1) synthesized by sucrose combustion process for high capacity lithium ion batteries

A mixed cathode material between Li₂MnO₃ and Li[Mn_1/3Ni_1/3Co_1/3]O₂ for high capacity lithium secondary batteries was introduced in this study. It was prepared using the sucrose combustion process because this is a simple process. The oxidation states of Mn, Co and Ni ions in the pristine Li[Li_(1−x)/3Mn_(2−x)/3Ni_x/3Co_x/3]O₂ compounds were confirmed to be tetravalent, trivalent and divalent, respectively, via XANES measurements. Electrochemical charge/discharge studies showed that the highest first discharge capacity of 224 mAh/g was obtained in composition of x = 0.5 at a 0.2 C rate. The oxidation state of the Co and Ni ions in the Li[Li_1/6Mn_1/2Ni_1/6Co_1/6]O₂ changed to higher oxidation states, but that of the Mn ions did not change.     

Crystal structure and EPR study of Mn-doped β-tricalcium phosphate

Mn-doped β-tricalcium phosphate was prepared by solid state reaction at 1100 °C. The crystal structure of Ca_2.85Mn_0.15(PO₄)₂, was determined by single crystal X-ray diffraction and found to be rhombohedral, R3c. Unit cell parameters are: a = 10.3419(3); c = 37.025(3) Å (hexagonal setting), Z = 21. Structure refinement data show that from the five Ca positions the Ca(4) site is only half filled and that the Mn²⁺ ions occupy the hexacoordinated Ca(5) site solely. EPR spectroscopy reveals that manganese in solid solutions Ca_3−xMn_x(PO₄)₂ (x = 0.1; 0.28; 0.6) is divalent and supports the structure refinement results that Mn occupies the Ca(5) site with a geometry very near to a regular octahedron.     

Structural and transport properties of stoichiometric Mn-doped magnetite: Fe3−xMnxO4

The polycrystalline samples of Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50) were prepared by a solid-state route reaction method. X-ray diffraction pattern shows that Mn²⁺ doped magnetites are in single phase and possess cubic inverse spinel structure. The resistivity measurements (10 < T < 300 K) for x = 0.0 and 0.01 confirms the first order phase transition at the Verwey transition T_V = 123 K and 117 K, respectively. No first order phase transition was evidenced for Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50). Small polaron model has been used to fit the semiconducting resistivity behavior and the activation energy ?_a, for samples x = 0.10 and 0.50 is about 72.41 meV and 77.39 meV, respectively. The Raman spectra of Fe_3−xMn_xO₄ at room temperature reveal five phonons modes for Fe_3−xMn_xO₄ (0.01 ≤ x ≤ 0.50) as expected for the magnetite (Fe₃O₄). Increased Mn²⁺ doping at Fe site leads to a gradual changes in phonon modes. The Raman active mode for Fe_3−xMn_xO₄ (x = 0.50) at ≅641.5 cm⁻¹ is shifted as compared to parent Fe₃O₄ at ≅669.7 cm⁻¹, inferring that Mn⁺² ions are located mostly on the octahedral sites. The laser power is fixed to 5 mW causes the bands to broaden and to undergo a small shift to lower wave numbers as well as increase in the full width half maxima for A_1g phonon mode with the enhancement of Mn²⁺ doping. Mössbauer spectroscopy probes the site preference of the substitutions and their effect on the hyperfine magnetic fields confirms that Mn⁺² ions are located mostly on the octahedral sites of the Fe_3−xMn_xO₄ spinel structure.     

R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb and Lu) and Lu3Mn3−3xCu2xVxO9: New noncentrosymmetric oxides related to YMnO3

We report formation of new noncentrosymmetric oxides of the formula, R₃Mn_1.5CuV_0.5O₉ for R = Y, Ho, Er, Tm, Yb and Lu, possessing the hexagonal RMnO₃ (space group P6₃cm) structure. These oxides could be regarded as the x = 0.5 members of a general series R₃Mn_3−3xCu_2xV_xO₉. Investigation of the Lu-Mn-Cu-V-O system reveals the existence of isostructural solid solution series, Lu₃Mn_3−3xCu_2xV_xO₉ for 0 < x ≤ 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn³⁺, Cu²⁺ and V⁵⁺ atoms that preserve the noncentrosymmetric RMnO₃ structure.     

Spectroscopic investigations and physical properties of Mn doped mixed alkali zinc borate glasses

Spectroscopic investigations on Mn²⁺ doped 20ZnO + xLi₂O + (30−x)Na₂O + 50B₂O₃ (5 ≤ x ≤ 25) (ZLNB) glasses reveal the non-linear behavior in their physical and structural properties. FT-IR spectra of ZLNB glasses reveal diborate units in the borate network. EPR spectra exhibit characteristic resonance signals of Mn²⁺ ions. A well resolved six line hyperfine structure around g = 2.02 corresponds to the sites of Type II, and a weak broad shoulder around g = 2.7 followed by an unresolved intense signal at g = 4.25 corresponding to sites of Type I are observed for their respective transitions. A large value of zero-field splitting parameter (D) is observed and it behaves non-linearly, reaches a maximum at x = 15 mol% with increase in Li₂O content. Δg values reveal the ionic nature of glass systems. Optical absorption spectra suggest the distorted octahedral site symmetry of Mn²⁺ ions in the host. Mixed alkali effect is evident in bandgap and Urbach energies.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Structure and surface morphology of Mn-implanted TiO2

A study of structure and surface morphology together with magnetic properties of Mn-implanted rutile-type TiO₂ single crystals is performed. Homogenous thin films of about 100 nm with different Mn_xTi_1 − xO₂ (x = 0.03; 0.05 and 0.07) chemical formula were obtained. The Mn ion implanted surface exhibited a dense microstructure with a nano grain size. The dependence of c/a axial ratio on manganese content suggests that Mn³⁺ species substituted tetragonal Ti⁴⁺. The annealing at 873 K caused changes in surface structure, morphology and roughness. A migration of manganese ions into the rutile single crystal takes place and in certain conditions Ti₂O phase occurs. Mn-implanted samples exhibit room temperature ferromagnetism and a Curie temperature of 680 K. Electron spin resonance analysis evidenced that manganese is incorporated by substitution as magnetically isolated Mn⁴⁺, Mn³⁺ and Mn²⁺ species. At 0.07% contents the Mn³⁺ species may enter in interstitial sites contributing to extinction of substitutional magnetic moment.     

Negative thermal expansion and electrical properties of Mn3(Cu0.6NbxGe0.4 − x)N (x = 0.05-0.25) compounds

Bulk materials with the general formula of Mn₃(Cu_0.6Nb_xGe_0.4 − x)N (x = 0.05, 0.1, 0.15, 0.2, 0.25), Mn₃(Cu_0.6Ge_0.4)N and Mn₃(Cu_0.7Ge_0.3)N were fabricated by mechanical ball milling and solid state sintering. Their thermal expansion coefficients and electrical conductivities were investigated in the temperature range of 80-300 K. It is found that the temperature interval of negative temperature expansion behavior is about 95 K in the samples of Mn₃(Cu_0.6Nb_0.15Ge_0.25)N and Mn₃(Cu_0.6 Nb_0.2Ge_0.2)N, which is twice as large as that of Mn₃(Cu_0.7Ge_0.3)N. The negative thermal expansion of Mn₃(Cu_0.6Nb_0.15Ge_0.25)N can reach to − 19.5 × 10⁻⁶ K^− 1 in the temperature range of 165 to 210 K. The electrical conductivity of this series materials is in a level of about 2.5 × 10⁶ (Ω m)^− 1.     

Influence of isovalent ion substitution on the electrochemical performance of LiCoPO4

LiCo_1−xM_xPO₄ (M = Mg²⁺, Mn²⁺ and Ni²⁺; 0 ≤ x ≤ 0.2) compounds have been synthesized by solid-state reaction method and studied as cathode materials for secondary lithium batteries. LiCoPO₄ exhibits a discharge plateau at ∼4.7 V with an initial discharge capacity of 125 mAh/g and on cycling capacity falls. Substitution of Co²⁺ with Mg²⁺/Mn²⁺/Ni²⁺ in LiCoPO₄ has an influence on the initial discharge capacity and on cycling behaviour. The capacity retention of LiCoPO₄ is improved by manganese substitution. Among the manganese substituted phases, LiCo_0.95Mn_0.05PO₄ shows good reversible capacity of ∼50 mAh/g.     

Synthesis and luminescence properties of color-tunable Ba1−ySryLa4−xTbx(WO4)7 (x = 0.02-1.2, y = 0-0.4) phosphors

Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ (x = 0.02-1.2, y = 0-0.4) phosphors were prepared via a solid-state reaction and their photoluminescence properties were investigated. An analysis of the decay behavior indicates that the energy migration between Tb³⁺ ions is conspicuous in the ⁵D₃ → ⁷F₄ transition due to the cross-relaxation in BaLa₄(WO₄)₇. A partial substitution of Ba²⁺ by Sr²⁺ can not only enhance the emission intensity but also increase the solid solubility of Tb³⁺ in Ba_1−ySr_yLa_4−xTb_x(WO₄)₇. The emission intensity of the ⁵D₄ → ⁷F_J (J = 4, 5, 6) transitions can be enhanced by increasing Sr²⁺ and Tb³⁺ concentrations, with the optimal conditions being x = 1.2, y = 0.4 (Ba_0.6Sr_0.4La_2.8Tb_1.2(WO₄)₇). Under near-UV excitation at 379 nm, the CIE color coordinates of Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ vary from blue (0.212, 0.181) at x = 0.04, y = 0, to green (0.245, 0.607) at x = 1.2, y = 0.4.     

Intense red-emitting phosphors for LED solid-state lighting

The phosphors Gd_2−xEu_x(MoO₄)₃ (x = 0.20, 0.40, 0.60, 0.80, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0), Gd_0.8−xY_xEu_1.2(MoO₄)₃ (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8) and Gd_0.2Y_0.6−xEu_1.2Sm_x(MoO₄)₃ (x = 0.02, 0.024, 0.028, 0.032, 0.036, 0.04) were prepared by solid-state reaction technique at 950 °C. The presence of the Y³⁺ and Sm³⁺ ions strengthen and broaden the absorption of the phosphors at ∼400 nm. The intense red-emitting phosphor Gd_0.2Y_0.572Eu_1.2Sm_0.028(MoO₄)₃ with orthorhombic structure was obtained. Both Eu³⁺ and Sm³⁺ f-f transition absorptions are observed in the excitation spectra, the main emission line is at 616 nm (⁵D₀ → ⁷F₂ transition of Eu³⁺) and the chromaticity coordinates (x = 0.66, y = 0.33) is very close to the NTSC standard values (x = 0.67, y = 0.33). It is considered to be an efficient red-emitting phosphor for GaN-based light emitting diode (LED).     

Enhanced multiferroic properties and tunable magnetic behavior in multiferroic BiFeO3-Bi0.5Na0.5TiO3 solid solutions

A series of multiferroic (1−x)BiFeO₃−x(Bi_0.5Na_0.5)TiO₃ (BF-BNT) (x = 0 − 0.6) solid solution ceramics were prepared by a sol-gel method. The XRD results show that increasing BNT content induce a gradual phase transformation from rhombohedral to pseudocubic structure near x = 0.4. Compared with pure BiFeO₃, superior multiferroic properties are obtained for x = 0.3 with remnant polarization P_r = 1.49 μC/cm² and saturated magnetization M_s = 0.51 emu/g. Importantly, the paramagnetic (PM) to ferromagnetic (FM) transition is observed for the solutions, and the Curie temperature (T_C) can be tuned by varying the content of BNT. This observed FM ordering is discussed in terms of the possible existence of the long-range superexchange interaction of Fe³⁺-O-Ti-O-Fe³⁺ in the chemically ordered regions.     

Luminescence of rare earth borosilicates with the stillwellite and related structures

By hydrothermal reactions it was possible to prepare well-crystallized borosilicates of composition La_{1 − x − y}Ln_xLn′_yBSiO₅ with the trigonal stillwellite structure. Ln = Eu³⁺ and Tb³⁺ produce compounds with only weak luminescence. Compounds with Ln = Ce³⁺ are strong UV phosphors with peak intensity at x = 0.08 and abrupt concentration quenching at x = 0.10. Compounds with Ln = Ce³⁺ and Ln′ = Tb³⁺ exhibit effective Ce³⁺ → Tb³⁺ coactivation and strong green luminescence. This family of borosilicates appears to be useful phosphor hosts, aside from the necessity of non-traditional synthesis.     

Electrical and optical properties of ZnO:Mn thin films grown by MOCVD

Diluted magnetic semiconductor epitaxial thin films of Zn_1 − xMn_xO have been grown on c-sapphire by the MOCVD technique. Variations of a and c lattice parameters follow Vegard's law and attest to the incorporation of substitutional Mn²⁺ ions. Carrier concentration (n-type) and electron mobility were studied versus temperature for different concentrations of manganese. Incorporation of manganese leads to the opening of the band gap, observed as a blue shift in energy regarding pure ZnO.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Synthesis and electrochemical properties of Ti doped Li3 − xFe2 − xTix(PO4)3/C cathode materials

Li_3 − xFe_2 − xTi_x(PO₄)₃/C (x = 0-0.4) cathodes designed with Fe doped by Ti was studied. Both Li₃Fe₂(PO₄)₃/C (x = 0) and Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C (x = 0.2) possess two plateau potentials of Fe³⁺/Fe²⁺ couple (around 2.8 V and 2.7 V vs. Li⁺/Li) upon discharge observed from galvanostatic charge/discharge and cyclic voltammetry. Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C has higher reversibility and better capacity retention than that of the undoped Li₃Fe₂(PO₄)₃/C. A much higher specific capacity of 122.3 mAh/g was obtained at C/20 in the first cycle, approaching the theoretical capacity of 128 mAh/g, and a capacity of 100.1 mAh/g was held at C/2 after the 20th cycle.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

A novel red long lasting phosphorescent (LLP) material β-Zn3(PO4)2:Mn, Sm

A novel red long lasting phosphorescent materials β-Zn₃(PO₄)₂:Mn²⁺,Sm³⁺ is firstly synthesized by high-temperature solid-state reaction. The influence of Sm³⁺ ions on luminescence and long lasting phosphorescence properties of Mn²⁺ in phosphor β-Zn₃(PO₄)₂:Mn²⁺,Sm³⁺ are systematically investigated. It is found that the red phosphorescence (λ = 616 nm) performance of Mn²⁺ ion such as brightness and duration is largely improved when Sm³⁺ ion is co-doped into the matrix in which Mn²⁺ ion acts as luminescent center and Sm³⁺ ion plays an important role of electron trap. Thermoluminescence spectrums show that there exists one peak in β-Zn₃(PO₄)₂:Mn²⁺,Sm³⁺, the depth of which is 0.33 eV, and that there are three peaks in β-Zn₃(PO₄)₂:Mn²⁺, among which the depth of the lowest temperature peak in β-Zn₃(PO₄)₂:Mn²⁺ is 0.37 eV. Such differences in the trap depth result in the improvement of red long lasting phosphorescence of Mn²⁺ in present matrix.