Study of the absorption edge pinning of Cd1−xMnxTe by transmission and piezotransmission measurements

It is known that a pinning of the fundamental absorption edge of Cd_1?xMn_xTe mixed crystals happened at x?0.5 implying a transition within 3d-(Mn²⁺) levels whereas the position of the fundamental absorption observed for x<0.5 is linear dependent of mole fraction x of manganese. Transmission and piezotransmission measurements are presented. They show that the two types of samples exhibit the same behaviour versus temperature and under pressure. We examine how these results affect the previous interpretations of the pinning phenomenon observed.     

Thermal dependence of impurity induced fluorescence in the system RbMgxMn1-xF3

The absorption spectrum of RbMnF₃ and the excitation spectra of the system RbMg_xMn_1-xF₃ at 10 K as well as the fluorescence spectra and lifetimes of Mn²⁺ in the systems RbMg_xMn_1-xF₃ and KMg_xMn_1-xF₃ in the region 10–300 K were measured. The lifetime and fluorescence temperature dependence suggest that the origin of the fluorescence occurs at Mn²⁺ sites slightly perturbed by impurity ions and that a non-radiative energy transfer mechanism is responsible for the observed thermal quenching. By using different Mn²⁺ concentrations in the above systems the dependence of the energy transfer on the Mn²⁺ concentration is shown. Finally, a preliminary observation on laser stimulated Mn²⁺ luminescence in the system RbMg_xMn_1-xF₃ is reported.     

Intracenter luminescence of Mn2+ in Cd1−x MnxTe and Cd1−x−y MnxMgyTe under intense optical pumping

A comparative analysis of the kinetic properties of intracenter 3d luminescence of Mn²⁺ ions in the dilute magnetic superconductors Cd_1?x Mn_xTe and Cd_1?x?y Mn_xMg_yTe is carried out. The influence of relative concentrations of the cation components on the position of the intracenter luminescence peak indicates that the introduction of magnesium enhances crystal field fluctuations. As a result, the processes facilitating nonlinear quenching of luminescence are suppressed. The kinetics of 3d-luminescence quenching in Cd_1?x Mn_xTe are accelerated considerably upon elevation of optical excitation level due to the evolution of cooperative processes in the system of excited manganese ions.     

Middle infrared luminescence of Tb in silver halide crystals and fibers

The optical absorption and the luminescence emission were investigated in AgCl_xBr_1−x crystals (0<x<1) doped with Tb³⁺ ions and in fibers extruded from these crystals. Strong luminescence emission in the middle infrared (MIR) in the spectral range 4.2-5.6 μm was observed for the first time in such crystals and fibers.¹ Various optical parameters were calculated for the Tb³⁺-doped crystals, using the Judd-Ofelt approximation. The measured and the calculated results have indicated that these doped crystals could be used for the development of solid-state lasers or fiber lasers operating in the middle infrared.     

Spectral studies on Mn ions doped in sodium-lead borophosphate glasses

Electron paramagnetic resonance (EPR), optical absorption, and luminescence spectral studies of Mn²⁺ ions doped in (30−x) (NaPO₃)₆+30PbO+40B₂O₃+xMnO₂ (x=1.0, 2.0, 3.0, 4.0, and 5.0 mol%) glasses have been studied. The EPR spectra exhibit resonance signals with effective g value at g_eff≈2.02 with six line hyperfine structure. A weak resonance signal with effective g value at g_eff≈4.3 is also observed for higher concentrations of Mn²⁺ ions. The EPR spectra of x =3.0 mol% of Mn²⁺ in sodium-lead borophosphate glass sample have been studied at various temperatures. It is observed that the resonance signal intensity decreases with increase in temperature. The optical absorption spectrum exhibits bands characteristic of Mn²⁺ ions in octahedral symmetry. From the analysis of the bands, the crystal-field parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. The emission spectrum exhibits single broad band in the green region.     

Optical properties and deep levels in annealed Si1−xMnx bulk materials

The optical properties and the deep levels in bulk Si_1−xMn_x formed by using an implantation and annealing method were investigated. Transmission electron microscopy, X-ray diffraction, and Hall-effect measurements showed that the annealed bulk Si_1−xMn_x samples were p-type crystalline semiconductors. The photoluminescence spectra for the annealed bulk Si_1−xMn_x material showed luminescence peaks corresponding to excitons bound to neutral acceptors and related to dislocations due to the existence of Mn impurities. Deep-level transient spectroscopy results for the annealed bulk Si_1−xMn_x showed deep levels related to the interstitial and substitutial sites of the Mn⁺ ions. These results can help improve understanding of the optical properties and the deep levels in annealed bulk Si_1−xMn_x material.     

Luminescence and vibration spectra of zinc manganese diphosphates

The synthesis conditions for new luminescent materials, zinc manganese diphosphates Zn_{2? x}Mn_xP₂O₇ · 5H₂O) (0 ≤ x ≤ 2.0), are considered. The photoluminescence and its excitation spectra, IR absorption, and Raman spectra of these materials are studied. The red luminescence band with a peak at about 700 nm is shown to be due to the radiative transitions in Mn²⁺ ions, which are set in an octahedral oxygen environment. The range of concentration quenching of Mn²⁺ ion radiation is determined. Correlation of the luminescent and vibration properties of these compounds is discussed.     

Photoacoustic method of determination of quantum efficiency of luminescence in Mn<Superscript>2+</Superscript> ions in Zn<Subscript>1−x−y</Subscript>Be<Subscript>x</Subscript>Mn<Subscript>y</Subscript>Se crystals

This paper presents step by step the procedure of determination of the quantum efficiency of luminescence of Mn²⁺ ions in the Zn_1−x−yBe_xMn_ySe crystals. The method is based on the photoacoustic spectroscopy approach. In the paper, the experimental spectra of absorbance, transmission, absorption and photoacoustic spectra of the samples are presented and analyzed from the point of view of the possibility of determination of the quantum efficiency of Mn²⁺ ion luminescence at room temperature. It was determined experimentally that in the investigated crystals the quantum efficiency of luminescence in the Mn²⁺ ions is about 35%, 40%, 32% for the absorption peaks at 430 nm, 470 nm, and 510 nm, respectively, for Zn_0.75Be_0.2Mn_0.05Se crystal.     

Magnetization and spin-flip energy in Cd0.9Mn0.1Se

Magnetization and spin-flip Raman measurements are reported for Cd_1?xMn_xSe, x = 0.106, at 1.9 < T < 4.2 K and magnetic fields H up to 80 kOe. The high-field results are combined to determine the exchange energy between donor electrons and Mn⁺⁺ spins, αN₀=261±13 meV. Empirical fits to the magnetization data are described.     

Electronic transport in the novel SOFC anode material La1−xSrxCr0.5Mn0.5O3±δ

Electronic conductivity in the potential SOFC anode material La_1−xSr_xCr_0.5Mn_0.5O_3±δ has been investigated in the range 0.2 < x < 0.3. log(σT) vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900 °C, conductivity in air increases with Sr²⁺ via an increase in [B_B] holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O₂), which is indicative of p-type conduction behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn³⁺, Mn⁴⁺ and oxygen, possibly due to co-existence of Mn²⁺, Mn³⁺ and Mn⁴⁺ via disproportionation as with La_1−xSr_xMnO_3±δ.     

The influence of Mn content on luminescence properties in Mn-doped ZnO films deposited by ultrasonic spray assisted chemical vapor deposition

Mn-doped ZnO (Zn_1−xMn_xO, 0 ≤ x ≤ 0.1) films are prepared by an ultrasonic spray assisted chemical vapor deposition method. X-ray diffraction and Raman scattering show that all the Zn_1−xMn_xO films are good wurtzite structures without any impurity phases. Cathodoluminescence spectra show that ultraviolet emission and green luminescence can be observed. The intensity of ultraviolet emission decreases with the increment of x, while the intensity of green luminescence increases with the increment of x when x ≤ 0.02. However, when x (x > 0.02) is further increased, the intensity of green luminescence decreases gradually, and the green luminescence disappears when x is above 0.075. We consider that the change of the luminescence is related to the competition between the radiative recombination and the non-radiative recombination.     

Pressure dependence of the absorption edge for Cd1-xMnxTe

The effect of pressure on the optical absorption edge of mixed crystals Cd_1-xMn_xTe with different manganese concentrations is reported. The observed absorption edge shifts to higher energy with increasing pressure at a rate of α=7?8×10^?3 eV/kbar and a second order coefficient of β=-4×10^?5 eV/kbar² for x<0.5, to lower energy with increasing pressure at a rate of α=-5.0 ×10^?3 eV/kbar for x?0.5. A phase transition occurs for all the samples studied. The absorption edge of the new phase is outside the wavenumber range of the instrument. The physical origins of different pressure coefficients are discussed in the light of the deformation potentials of energy band states and the hybridization of the Mn²⁺ 3d levels with the p-like states in the valence band.     

Exciton and intracenter radiative recombination in ZnMnTe and CdMnTe quantum wells with optically active manganese ions

The emission spectra of Zn_1?x Mn _x Te/Zn_0.6Mg_0.4Te and Cd_1?x Mn _x Te/Cd_0.5Mg_0.5Te quantum-well structures with different manganese concentrations and quantum-well widths are studied at excitation power densities ranging from 10⁵ to 10⁷ W cm^?2. Under strong optical pumping, intracenter luminescence of Mn²⁺ ions degrades as a result of the interaction of excited managanese ions with high-density excitons. This process is accompanied by a strong broadening of the emission band of quantum-well excitons due to the exciton-exciton interaction and saturation of the exciton ground state. Under pumping at a power density of 10⁵ W cm^?2, stimulated emission of quantum-well excitons arises in CdTe/Cd_0.5Mg_0.5Te. The luminescence kinetics of the quantum-well and barrier excitons is investigated with a high temporal resolution. The effect of the quantum-well width and the managanese concentration on the kinetics and band shape of the Mn²⁺ intracenter luminescence characterized by the contribution of the manganese interface ions is determined.     

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.     

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.     

Effect of allied and alien ions on the EPR spectrum of Mn-containing lithium-manganese spinel oxides

Electron paramagnetic resonance spectroscopy was used for studying the effect of allied and alien ions on the EPR spectrum of Mn⁴⁺-containing lithium-manganese spinel oxides. Manganese spinel oxides with paramagnetic Mn⁴⁺ and diamagnetic substituents in the 16d spinel sites were studied: Li[Mg_0.5Mn_1.5]O₄, Li[Mg_0.5−xCo_2xMn_1.5−x]O₄, 0<x≤0.5, and Li[Li_1/3Mn_5/3]O₄. Ni²⁺-ions with integer-spin-ground state (S=1) were selected as alien ions: Li[Mg_0.5−xNi_xMn_1.5]O₄ (0≤x≤0.5), Li[Li_(1−2x)/3Ni_xMn_(5−x)/3]O₄ (0≤x≤0.5), and Li[Ni_0.5Mn_1.5−yTi_y]O₄ (0≤y≤1.0). It was shown that in Ni-substituted oxides the low temperature EPR response comes from magnetically correlated Ni-Mn spins, while at high registration temperature Mn⁴⁺ ions give rise to the EPR profile. Analysis of the EPR line width allows differentiating between the contributions of the density of paramagnetic species and the strength of the exchange interactions in magnetically concentrated systems. The density of allied and alien paramagnetic species has no effect on the EPR line width in cases when the strengths of antiferro- and ferromagnetic interactions on an atomic site are close. On the contrary, when antiferro- or ferromagnetic interactions on an atomic site are dominant, the EPR line width increases with the density of paramagnetic species.     

Electronic structure and magnetic properties of BaTi1-xMnxO3

The electronic structure and magnetic properties of polycrystalline BaTi_1-xMn_xO₃ (x = 0–0.1) compounds prepared by solid-state reactions were studied. The results revealed that the increase in Mn content (x) did not change the oxidation numbers of Ba (+2) and Ti (+4) in BaTi_1-xMn_xO₃. However, there is the change in Mn valence that Mn^3+,4+ ions coexist in the samples with x = 0.01–0.04 while Mn⁴⁺ ions are almost dominant in the samples with x = 0.06–0.1. We also point out that Mn³⁺ and Mn⁴⁺ ions substitute for Ti⁴⁺ and prefer locating in the tetragonal and hexagonal BaTiO₃ structures, respectively, in which the hexagonal phase constitutes soon as x = 0.01. Particularly, all the samples exhibit room-temperature ferromagnetism. Ferromagnetic order increases with increasing x from 0 to 0.02, but decreases as x ≥ 0.04. We think that ferromagnetism in BaTi_1-xMn_xO₃ is related to lattice defects and/or exchange interactions between Mn³⁺ and Mn⁴⁺ ions.     

The behavior of Shubinikov-de Haas oscillations in Hg1−x−yCdxMnyTe alloys

The transverse and longitudinal magnetoresistance are measured on a quaternary semimagnetic semiconductor, n-type Hg_1−x−yCd_xMn_yTe with 0.01 < x < 0.23 and y ≈ 0.14, at different temperatures. The peaks of the Landau-spin states are assigned using the selection rules already developed for HgCdTe. The Landau-spin states are modified by an exchange interaction between the Mn²⁺ ions localized spin and the band electrons, thus it becomes possible to compare directly the extent of the spin modification between the negative gap side and the open gap side of the new alloys.     

Synthesis and magnetic properties of hexagonal Y(Mn,Cu)O3 multiferroic materials

Single-phase hexagonal-type solid solutions based on the multiferroic YMnO₃ material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn_1−xCu_xO₃; x<0.15) and self-doping at the A-site (Y_1+yMnO₃; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn³⁺ two-dimensional lattice. The magnetic transition at T_N decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn³⁺-Mn⁴⁺ interactions created by the substitution of Mn³⁺ by Cu²⁺, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn³⁺-Mn⁴⁺ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.     

Magnetocrystalline anisotropy and inversion degree of manganese-ferrous-ferrites

Torque measurements have been performed at 4 and 77 K on single crystals of Mn_1?xFe_2+xO₄ (0<x<0.05) and MnFe_2?xTi_xO₄ (0<x<0.1). The crystals were either quenched or slowly cooled causing a change of inversion by 0.1. It is found that the magnetic anisotropy due to the ferrous ions in the Ti-doped samples is 80 per cent larger than in the Mn_1?xFe_2+xO₄ crystals. In both crystal series the ferrous ion anisotropy in the slowly cooled crystals is 70 per cent higher than in the quenched crystals. The K₁ of MnFe₂O₄ at 4 K is found to decrease from ?3.6 × 10⁵ erg/cm³ after show cooling, down to ?2.6 × 10⁵ erg/cm³ after quenching.