Studies on the synthesis and characterization of Zn1− x Cd x S and Zn1− x Cd x S:Mn2+ semiconductor quantum dots

Quantum dots (3–4?nm) of Zn_{1? x} Cd _x S (both free of Mn²⁺ and with Mn²⁺ incorporated) were synthesized through a novel solvothermal-microwave irradiation technique. Detailed structural analysis of the Zn_{1? x} Cd _x S and Zn_{1? x} Cd _x S:Mn²⁺ (x?=?0, 0.25, 0.5, 0.75 and 1) materials was carried out using powder X-ray diffraction technique. For all the compositions, the crystallite size was controlled to less than 1.5?nm. The optical energy gap for Zn_{1? x} Cd _x S was found to vary from 3.878 to 2.519?eV and for Zn_1?x Cd _x S:Mn²⁺ it varies from 3.830 to 2.442?eV when x is increased from 0 to 1. Overall, the optical energy gap could be tuned from a minimum of 2.442?eV to a maximum of 3.878?eV. DC conductivity analysis (from 40°C to 150°C) and electrical energy gap analysis for all the compositions were also performed. The dc conductivity for Zn_{1? x} Cd _x S solid solutions varies from 0.3840?×?10^?10 to 8.7782?×?10^?10?mho/m at 150°C and for Zn_{1? x} Cd _x S:Mn²⁺ it varies from 0.5751?×?10^?10 to 9.8078?×?10^?10 mho /m at 150°C (for x?=?0 to x?=?1). The method of synthesis and the results observed in this investigation may assist in the fabrication of optical devices when the required operational performance falls under the range observed in the study.     

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.     

The migration of Mn2+ ions in Cd1−xMnxS nanocrystals: Thermal annealing control

This work reports evidence of the induced migration of Mn²⁺ ions in Cd_(1?x)Mn_xS nanocrystals (NCs) by selecting a specific thermal treatment for each sample. The growth and characterization of these magnetic dots were investigated by atomic force microscopy (AFM), optical absorption (OA), and electronic paramagnetic resonance (EPR) techniques. The comparison of experimental and simulated EPR spectra confirms the incorporation of Mn²⁺ ions both in the core and at the dot surface regions. The thermal treatment of a magnetic sample, via selected annealing temperature and/or time, affects the fine and hyperfine interaction constants which modify the shape and the intensity of the EPR transition spectrum. The identification of these changes has allowed tracing the magnetic ion migration from core to surface regions of a dot as well as inferring the local density of the magnetic impurity ions.     

Comparison of electron spin polarization of P 870 + Qa a − observed in Zn2+-containing and Fe2+-depleted bacterial reaction centers

Recently, a general model has been developed to explain electron spin polarized (ESP) electron paramagnetic resonance (EPR) signals found in systems where radical pairs are formed sequentially. The photosynthetic bacterial reaction center (RC) is such a system in which we can experimentally vary parameters (lifetime, structure, and magnetic interactions in the sequentially formed radical pairs) that affect ESP development in order to test this model. In Fe²⁺-depleted transfer step from intermediate radical pair, P ₈₇₀ ⁺ Q _a ^? which is produced in an electron transfer step from intermediate radical pair, P ₈₇₀ ⁺ I^?. (P ₈₇₀ ⁺ is the oxidized primary donor, a special pair of bacteriochlorophyll molecules, I^? is the reduced bacteriopheophytin acceptor, and Q _a ^? is the reduced primary quinone acceptor.) The lifetime of P ₈₇₀ ⁺ I^? can be shortened relative to the lifetime of P ₈₇₀ ⁺ I^? in Fe²⁺-depleted RCs by substitution of Zn²⁺. We report the first observation of X-band and Q-band ESP EPR signals due to P ₈₇₀ ⁺ Q^? from bacterial reaction centers that contain Zn²⁺. Comparison of these signals to those observed from Fe²⁺-depleted bacterial reaction centers shows intensity differences and g-factor shifts. The results are discussed in terms of the general sequential radical pair model.     

Photoconductivity and photoluminescence in chemically deposited films of (Cd–Zn)S:CdCl2, Ho

Results of SEM, XRD, optical absorption/reflectance, photoconductivity (PC), and photoluminescence (PL) are presented for (Cd–Zn)S:CdCl₂, Ho films prepared by chemical deposition technique by direct dipping either at room temperature (RT) or at 60 °C in a water bath. SEM studies show the presence of non-uniform distribution of particles. XRD studies show lines of CdS, ZnS along with lines of CdCl₂ and Ho. PL is found to be pronounced in films of RT preparation and for those prepared at 60 °C, PC is higher. Optical absorption/reflectance studies show the presence of Ho corresponding to the transition ⁵I₈→⁵F₁/⁵G₆. Emissions corresponding to the transitions ⁵S₂/⁵ F₄→⁵ I₈, ⁵G₅→⁵I₇, and ³H₅→⁵I₈ are observed in PL emission spectra.     

Luminescence of Eu2+–vc− dipoles and their associates in CsI:Eu crystals

Spectral-kinetics properties of photo-scintillation excited with single light pulses of a nitrogen laser (λ=337.1 nm, t_1/2=5 ns, Q=1 mJ) have been studied in CsI:Eu crystals at temperature within 80–300 K. It is found that the exponential decay of 463 nm emission band has a time constant which grows from 0.85 μs at 78 K to 1.6 μs at 380 K. Such an anomalous temperature behavior of 463 nm emission decay kinetics is discussed in terms of the crystal thermal expansion. It has been proposed that 463 nm emission is caused by a cluster center consisting of three dipoles Eu²⁺v_c^? bounded with each other in a hexagon. Owing to the exchange resonance in the cluster, the energy passes from an excited dipole to a non-excited one and the distance between them gets longer due to thermal expansion of the crystal.     

Observation of magnetic order of Cu-moment aroundx=0.12 in La2−x Ba x CuO4 and La2−x sr x CuO4 by μ+SR

Zero field positive muon spin rotation method ( ⁺SR) is applied on La_2–x Sr _x CuO₄ around forx=0.12 at which the high-T _c superconductivity (SC) is suppressed. The magnetically ordered state of Cu-moments, which is not a spin glass state but an antiferromagnetic like state, appears below 15 K for 0.105x0.120. The magnetic phase boundary is very similar to the one of the La_2–x Ba _x CuO₄ in which the structural transition from the low temperature orthorhombic (LTO) phase to the low temperature tetragonal (LTT) phase is observed aroundx=0.12. The present study suggests that there is no big difference of the electronic state of the CuO₂ plane between the La-Ba system and the La-Sr system and that the magnetic ordering of Cu-moments plays an important role for the suppression of the high-T _c SC aroundx=0.12 in both of the systems, although the LTO-LTT structural transition has not been observed yet in the La-Sr system.     

The primary and secondary acceptors in bacterial photosynthesis: II. The structure of the Fe2+-Q− complex

The primary processes of bacterial photosynthesis take place in a membrane-bound protein called the reaction center (RC). The process involves light-induced electron transfer from a primary electron donor to a sequence of electron acceptors. The terminal acceptors, operating sequentially, are two ubiquinones, Q_A and Q_B, that couple magnetically to a high-spin (S = 2) Fe²⁺ forming an Fe²⁺-Q^? complex. We have used a variety of techniques to investigate the electronic as well as some features of the spatial structure of the Fe²⁺-Q^? complex in RCs fromRb. sphaeroides. These include: (a) static magnetization measurements in the temperature range of 0.7 to 190 K and magnetic fields up to 8 kG, (b) EPR spectroscopy at helium temperatures at 1.2, 9, and 35 GHz, (c) Mössbauer spectroscopy and (d) extended X-ray fine structure (EXAFS) determinations. The results of these measurements showed that Fe²⁺ resides in an asymmetric ligand field environment forming 6 ligands with a combination of oxygens and nitrogens. From the EXAFS results the distances of the Fe²⁺ to the first and third coordination shells were determined. These spatial features were subsequently corroborated by the X-ray structure of the RC, which showed the environment of the Fe to be a distorted octahedron, the base plane of which is formed by three N_?’s of histidines and one carbonyl oxygen; the apex is formed by a fourth N_? and a second carbonyl oxygen. The distances from the Fe²⁺ to the first and third shell were in good agreement with the values obtained from EXAFS. The most detailed information of the electronic structure of the Fe²⁺-Q^? complex was obtained from the EPR spectra using the spin Hamiltonian formalism. The following spin-Hamiltonian parameters were obtained: for the crystalline field parameters,D = 7.60 K,E/D = 0.25; for the electronicg-values, g_{Fe, x} = 2.16, g_{Fe, y} = 2.27, g_{Fe, z} = 2.04 and for the antiferromagnetic exchange interaction,J _x = ?0.13 K,J _y = ?0.58 K,J _z = ?0.58 K. The use of the spin Hamiltonian was validated by comparing the results obtained from it with those obtained from an exact numerical solution of the 25 lowest energy levels of the orbital Hamiltonian. Possible roles that Fe²⁺ may play in the function of the RC are discussed. They include a structural role in which Fe²⁺ liganded to four histidine nitrogens imparts a rigid structure to a four α-helix bundle and a role in the electron transfer kinetics, most notably from the intermediate acceptor I^? (bacteriopheophytin) to Q_A. Replacement of Fe²⁺ by diamagnetic Zn²⁺ retained all observed native characteristics of the RC.     

Generation of nanosecond 2.65μm pulses and pulse narrowing in fiber-bulk Ho3+:YAG laser pumped gain-switched Cr^2+:Cd Se laser

The generation of mid-infrared pulsed lasers was achieved in a Ho3+:YAG laser pumped gain-switched Cr^2+:Cd Se laser system with the shortest pulse duration of 4.15 ns.With a pump pulse duration of 50 ns and pump power of 2.7 W,the gain-switched Cr^2+:Cd Se laser achieved over 10 times pulse narrowing,obtaining the maximum peak power of 5.7 k W.The optical-to-optical conversion efficiency was 3.7%,which could be further improved with better crystal surface polishing quality.The laser central wavelength was measured to be 2.65μm with a bandwidth(FWHM)of 50 nm.In addition,the parameter optimization for suppressing the pulse tail was discussed,while the long cavity and high output transmissivity contributed to obtaining the single-peak pulses.     

Structural and electronic properties of Fe 3+ -O 2− Pairs in KMF 3 lattices (M=Mg,Zn): Is the superposition model valid?

The geometrical and electronic properties of the tetragonal FeF 5 O 4 m complex which is likely formed in KMgF 3 and KZnF 3 fluoroperovskites have been investigated by means of Density Functional calculations. The properties of this centre are dependent on the Fe-O distance ( R ox ) and also on the distances R eq and R ax between Fe 3+ and the four equatorial F m ions and the apical F m ion respectively. The calculated equilibrium distance for the isolated Fe 3+ -O 2 m pair is equal to R ox =1.63 v + while when it is introduced in KMF 3 lattices ( M =Mg, Zn) R ox ～1.82 v + . Compared to FeF 6 3 m in KMgF 3 ( R eq = R ax =1.94 v + ) the obtained equilibrium distances R ax =2.05 v + and R eq =2.02 v + mean an outwards relaxation of 6% and 4% respectively induced by the F m M O 2 m substitution. The ratio of the associated superhyperfine ( shf ) constants of equatorial ( A eq ) and axial ( A ax ) F m ligands is A eq / A ax , 2 and thus account for an experimental fingerprint of this centre. The huge difference between A s (eq) and A s (ax) cannot be explained assuming that the law relating A s to the metal-ligand distance, R , for the octahedral FeF 6 3 m unit can be transferred to the present case involving a lower symmetry . The present analysis casts doubts on the conclusions previously reached using the empirical superposition model.     

Inversion of spin levels in Ni2+: Zn(BF4)2 · 6H2O under uniform compression and the effect of transition coincidence

The electron paramagnetic resonance (EPR) spectra of Ni²⁺ ions substituting for Zn²⁺ ions in Zn(BF₄)₂ · 6H₂O crystals are studied over a wide range of temperatures under uniform compression. Measurements are performed in the X-and Q-bands. The parameter D, which characterizes the initial splitting, undergoes considerable variations with changes in temperature and pressure, whereas the g factor remains virtually unchanged. An increase in the temperature is accompanied by a nonlinear increase in D. Under uniform compression, the initial splitting varies linearly and the parameter D changes its sign at 3.5 kbar, which indicates inversion of the spin levels. The coincidence of the EPR lines associated with different transitions leads to the appearance of line-profile dips in the spectra due to cross-relaxation inside the spin system.     

Isospin decomposition of 0+ → 2+ and 0+ → 3− transition matrix elements by Coulomb nuclear interference observed in inelastic α-scattering from the even Zr isotopes

Coulomb-nuclear interference in inelastic scattering of 35.4 MeVα-particles from the stable even Zr isotopes was studied. In the framework of a collective DWBA analysis isoscalar and electromagnetic transition rates for low lying 2⁺ and 3^? states were derived. The experimentalB (E2) values are in good agreement with results obtained by purely electromagnetic methods. The deducedM _n /M _p ratios of the 2 ₁ ⁺ levels exhibit a surprisingly large increase with increasing neutron number.     

Enhanced red fluorescence in Sr2Si1−xGexO4:Eu3+ phosphors by the substitution of Si by Ge for white light emitting diodes

Eu³⁺-doped Sr₂Si_1?xGe_xO₄ (x=0–1) phosphors have been prepared by the high temperature solid-state reaction method. The luminescent properties of these phosphors were investigated. Red fluorescence of Eu³⁺ is enhanced gradually in the samples with increasing substitution of Si by Ge upon the excitation of 393 nm light. The intensity is increased by 50% with full substitution of Si by Ge. These results are originated from the structural changes and the phonon energy reduction in the samples due to the substitution of Si by Ge. The CIE chromaticity coordinates of the phosphors vary slightly around (0.62, 0.37) and all are in the red color region. The results indicate that these phosphors could be promising red phosphors for white light emitting diodes.     

Effects of Cd2+ substitution on elastic properties and step-like anomalies in Tl0.9Bi0.1Sr1.8Yb0.2Ca1−xCdxCu1.99Fe0.01o7−δ superconductors

Cd-doped Tl_0.9Bi_0.1Sr_1.8Yb_0.2Ca_1−xCd_xCu_1.99Fe_0.01O_7−δ (x=0–0.4) bulk superconductor samples were prepared by solid-state reaction method, to examine the effect of Cd on ultrasonic velocity and elastic behavior of the samples. The samples were characterized by X-ray diffraction, DC electrical resistivity and temperature dependent ultrasonic velocity measurements. DC electrical resistivity measurement showed all the samples exhibit metallic normal-state behavior with the highest T_{c zero} observed at around 76.4 K (x=0.3). Ultrasonic velocity measurements at 80 K showed a non-linear increase in both absolute longitudinal and shear velocities as well as elastic moduli with Cd substitution with the largest increase observed for the x=0.3 sample. Temperature dependant longitudinal modulus showed elastic anomaly characterized by a step-like slope change at around 230 K for x=0 & x=0.3 and at around 250 K for x=0.4 with the x=0.3 sample showing the sharpest slope change. A comparison between experimental data and calculated lattice anharmonicity curve based on the model proposed by Lakkad, showed large deviation of the experimental longitudinal modulus curves for (x=0.3) from the calculated anharmonicity curves indicating that the elastic behavior was strongly influenced by the existence of the step-like longitudinal anomaly. On the other hand, our analysis using the Landau free energy model found that the anomalous step-like elastic behavior fitted well with the equation derived from the model for regions below and above the elastic anomaly temperature, T_A. The fitting indicated that the anomaly is related to a phase transition that is suggested to involve ordering of oxygen which introduces strain in the system.     

Different coordination geometries of Co(II) ion in CoxZn1−xIn2S4 and CoGaInS4 layer compounds: A quantitative determination by XPS

A quantitative determination of tetrahedral and octahedral cobalt ions in layer ternary compounds is obtained by the analysis of the photoelectronic spectra. This method can be of general application for computing a quantitative distribution of paramagnetic ions between different coordination geometries.