X-ray photoelectron spectroscopy characterization of the layered intercalated compound K2xMn1 − xPS3

Polycrystalline powders of the layered MnPS₃ compound have been intercalated with K⁺ ions by ion-exchange to yield the K_2xMn_1 − xPS₃ intercalate. X-ray photoelectron spectroscopy has been applied to learn about the electronic structure of this compound. In particular, we have studied the XPS spectra of the Mn 2p and 3p, P and S 2p, K 2p and 3p core levels and of the valence band region. The binding energies for various core levels of the elements present in this compound and their observed chemical shifts are analyzed. The data give evidence for the lack of non-equivalent atoms of K, Mn, P and S. Shake-up satellites are present at the Mn 2p and 3p core levels. The occurrence of such lines allows us to hypothesize that K_2xMn_1 − xPS₃ is a large-gap insulating Mn compound. Confirmation that only an ion transfer accompanies the intercalation process is given from both the strong observed similarity with the corresponding XPS spectra in MnPS₃ and the observed binding energy positions of the K 2p and 3p levels. As regards the valence band XPS spectrum, the observed analogies with the corresponding XPS spectra of the pure compound and of other K compounds have allowed us to single out two regions and their probable contributors.     

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.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

Magnetic properties and charge ordering in Pr0.75Na0.25MnO3 manganite

The structural and magnetic properties of Pr_0.75Na_0.25MnO₃ have been investigated experimentally. At room temperature, the compound shows paramagnetic characteristic. Along with decreasing temperature, a peak appears in the magnetization versus temperature curve around 220 K. To clarify whether this peak is associated with the ordering arrangement of Mn³⁺ and Mn⁴⁺ ions, electron diffraction experiments were carried out below and above 220 K respectively. Only basic Brag diffraction spots can be observed at high temperatures, however, superlattice diffraction appears below 220 K. This provides direct evidence for the existence of charge ordering in Pr_0.75Na_0.25MnO₃. We find the Mn³⁺ and Mn⁴⁺ cations form zigzag chains in a-c plane by analyzing the diffraction patterns. Combining with the magnetization measurements and the results of electron spin resonance, we confirm the antiferromagnetic phase and ferromagnetic component coexist in Pr_0.75Na_0.25MnO₃ below 120 K.     

Magnetic properties of electron-doped Y1−xCexMnO3 compounds

Cerium-doped Y_1−xCe_xMnO₃ compounds have been prepared in single-phase form for x=0 to 0.10. X-ray diffraction (XRD) patterns could be analyzed by using P6₃cm space group. Temperature variations of ac susceptibility and magnetization measurements show that these Ce-doped materials exhibit weak ferromagnetic transition. The observed ferromagnetic transition is attributed to the double exchange ferromagnetic interaction between Mn²⁺ and Mn³⁺ ions due to electron doping. The M–H loops exhibit hysteresis along with linear contribution and were analyzed based on bound magnetic polaron (BMP) model. Increase in saturation magnetization and decrease in BMP concentrations have been observed with increase in Ce doping.     

The effect of Cu substitution on the A1g mode of La0.7Sr0.3MnO3 manganites

We report on the first Raman data of Cu substituted La_1−ySr_yMn_1−xCu_xO₃ (0≤x≤0.10 and 0.17≤y≤0.3, accordingly in order to have the same Mn⁴⁺/[Mn⁴⁺+Mn³⁺] ratio), collected in the frequency range 100-900 cm⁻¹ and at room temperature, with parallel (e_i∥e_s) and crossed (e_i⊥e_s) polarizations of the incident (e_i) and scattered (e_s) light. Spectra were fitted with a Drude-Lorentz model, and peaks at 190-220 and 430 cm⁻¹, together with two broad structures centered at near 500 and 670 cm⁻¹, have been found. We also have observed that the A_1g mode is substantially shifted with increasing Cu substitution. The A_1g phonon shift is a linear function of the tolerance factor t and the rhombohedral angle α_r, thus following the structural changes of the MnO₆ octahedra in the system.     

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.     

Synthesis,structure and magnetic properties of layered manganate Sr4Mn3−xCrxO10 (x=0, 0.2)

The manganates Sr₄Mn_3−xCr_xO₁₀ (x=0 and 0.2) have been synthesized by solid state reaction. Powder X-ray diffraction analysis shows orthorhombic symmetry with space group Cmca for both compounds. The magnetic susceptibility measurements show an antiferromagnetic transition at 192 and 176 K for x=0 and 0.2, respectively. The magnetic susceptibility data were estimated using a model based on spin exchange antiferromagnetic interactions in isolated (Mn⁴⁺) trimer; a paramagnetic contribution due to the chromium ions was added in the case of Cr-doped materials.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

X-ray photoelectron spectroscopic investigations on cubic BaTiO3, BaTi0.9Fe0.1O3 and Ba0.9Nd0.1TiO3 systems

X-ray photoelectron spectroscopic (XPS) studies were carried out on wet-chemically synthesized cubic BaTiO₃, Ba_0.9Nd_0.1TiO₃ and BaTi_0.9Fe_0.1O_3−δ powders. The compounds were prepared by hydrothermal and gel to crystallite conversion technique; and phases formed readily at 420 K. The phase purity of the powders was confirmed from X-ray diffractometry. Chemical state and chemical environment of the constituent elements in the compositions were examined by XPS. Ba²⁺ was found to exist in two different chemical environments in these titanates. The Ti 2p_3/2 photoelectron peak in BaTi_0.9Fe_0.1O_3−δ was found to be broadened after Fe³⁺ substitution. Any resolvable broadening was not observed distinctly in the Ti 2p peak for Ba_0.9Nd_0.1TiO₃, unsintered BaTiO₃ and BaTiO₃ annealed in hydrogen (8% H₂ + Ar) at 1000 K. The prevalence of mixed-valent titanium and iron in BaTi_0.9Fe_0.1O_3−δ composition was evident from the XPS results and was further supported by the enhanced electrical conductivity at 298-550 K for BaTi_0.9Fe_0.1O_3−δ in comparison to BaTiO₃ and Ba_0.9Nd_0.1TiO₃. Hydroxyl incorporation was facilitated by substituting Nd³⁺ in Ba-sublattice. The presence of hydroxyls was observed from the broadening of the O 1s peak in XPS studies of the compounds.     

High temperature and low current density synthesis of Mn3O4 porous nano spheres: Characterization and electrochemical properties

Uniform and single-crystalline Mn₃O₄ nano-spheres were synthesized by cathodic electrodeposition at high temperature (80 °C) and low current density (0.25 mA cm⁻¹) on steel electrode. Further the annealed samples were characterized for their structural and morphological properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) studies. TEM and SEM images showed that particles have spherical shapes and the average diameter size was about 50 nm. Formation of Mn₃O₄ compound was confirmed from FTIR studies. The XRD pattern showed that the Mn₃O₄ exhibit tetragonal hausmannite structure. The results of N₂ adsorption-desorption analysis indicated that Mn₃O₄ nano-sphere has BET surface area of about 177.6 m² g⁻¹ and average pore diameters of 3 and 4 nm. The possible formation mechanism of Mn₃O₄ nanostructures has been discussed. The supercapacitive properties of Mn₃O₄ sample in 0.5 M Na₂SO₄ electrolyte showed maximum supercapacitance of 235.4 Fg⁻¹ at scan rate 10 mV s⁻¹. Coulumbic efficiency could be kept about 90% during 1000 cycles at 10 mV s⁻¹.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

Charge order melting and magnetic transition in Nd0.5(1+x)Ca0.5(1−x)Mn(1−x)CrxO3 system

The magnetic property of double doped manganite Nd_0.5(1+x)Ca_0.5(1−x)Mn_(1−x)Cr_xO₃ with a fixed ratio of Mn³⁺:Mn⁴⁺=1:1 has been investigated. For the undoped sample, it undergoes one transition from charge disordering to charge ordering (CO) associated with paramagnetic (PM)-antiferromagnetic (AFM) phase transition at T<250 K. The long range AFM ordering seems to form at 35 K, rather than previously reported 150 K. At low temperature, an asymmetrical M-H hysteresis loop occurs due to weak AFM coupling. For the doped samples, the substitution of Cr³⁺ for Mn³⁺ ions causes the increase of magnetization and the rise of T_c. As the Cr³⁺ concentration increases, the CO domain gradually becomes smaller and the CO melting process emerges. At low temperature, the FM superexchange interaction between Mn³⁺ and Cr³⁺ ions causes a magnetic upturn, namely, the second FM phase transition.     

A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application

Mn₃O₄ thin films have been prepared by novel chemical successive ionic layer adsorption and reaction (SILAR) method. Further these films were characterized for their structural, morphological and optical properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), field emission scanning electron microscopy (FESEM), wettability test and optical absorption studies. The XRD pattern showed that the Mn₃O₄ films exhibit tetragonal hausmannite structure. Formation of manganese oxide compound was confirmed from FTIR studies. The optical absorption showed existence of direct optical band gap of energy 2.30 eV. Mn₃O₄ film surface showed hydrophilic nature with water contact angle of 55°. The supercapacitive properties of Mn₃O₄ thin film investigated in 1 M Na₂SO₄ electrolyte showed maximum supercapacitance of 314 F g⁻¹ at scan rate 5 mV s⁻¹.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Effects of Mn substitution of Co and Fe in spinel CoFe2O4 thin films

Effects of Mn substitution for Co and Fe on the structural and magnetic properties of inverse-spinel CoFe₂O₄ have been investigated. Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ thin films were prepared by a sol–gel method. The observed increase of the lattice constant of Mn_xCo_1−xFe₂O₄ indicates that Mn²⁺ ions substitute the octahedral Co²⁺ sites. Conversion electron Mössbauer spectroscopy data indicate that a fraction of octahedral Co²⁺ ions exchange sites with tetrahedral Fe³⁺ ions through Mn doping. Vibrating-sample magnetometry data exhibit a large increase of saturation magnetization for both Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ films compared to that of the CoFe₂O₄ film. Such enhancement of magnetization can be explained in terms of a breaking of ferrimagnetic order induced by the Co²⁺ migration.     

Inelastic magnetic X-ray scattering from highly correlated electron systems: La1.2Sr1.8Mn2O7, La0.7Sr0.3MnO3 and Fe3O4

Magnetic Compton profiles have been measured for the colossal magnetoresistance manganites La_1.2Sr_1.8Mn₂O₇ and La_0.7Sr_0.3MnO₃, and for magnetite Fe₃O₄, along various crystallographic directions, over a wide range of temperatures and magnetic fields. The experimental results are interpreted via first-principles computations for the double layer manganite, La_1.2Sr_1.8Mn₂O₇, and by using a simple model involving atomic d-orbitals and free electrons for the other two compounds. For all three materials a preference for the occupation of e_g orbitals is found, particularly, for orbitals of dx²−y² symmetry. An itinerant electron contribution is adduced at all temperatures in magnetite; such a contribution also appears in La_1.2Sr_1.8Mn₂O₇, but it is present only at low temperatures in La_0.7Sr_0.3MnO₃.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Effect of illumination on magnetization and microwave absorption of La1−xCaxMnO3 (x<0.2) films

Light-induced changes of the hysteresis loops of magnetization and microwave absorption are investigated in low-doped La_1−xCa_xMnO₃ (x<0.2) thin films. The width of the hysteresis loops decreases clearly under illumination with visible or near-infrared light at temperatures below 50 K. The microwave conductivity has a minimum value at magnetic fields corresponding to the magnetization reversal and is shifted towards weaker fields under illumination. These effects show complex nonexponential time evolution and dependence on strength of the magnetic field. The results can be explained by assuming that small ferromagnetic metallic regions exist within the insulating ferromagnetic phase of the sample, and that these regions are expanded by optically induced charge transfer between Jahn–Teller split e_g states of neighboring Mn³⁺ ions. Decrease of the Mn³⁺ XPS core level spectrum is observed in the samples under illumination with a HeNe laser.