Temperature dependence of photoluminescence and electroluminescence of ZnS:Mn crystals

By means of comprehensive analysis of the temperature dependences of the photoluminescence for ZnS:Mn crystals, we have observed persistent changes in the intensity, shape, and position of the maximum in the emission spectrum associated with changes in the immediate environment of the manganese luminescence centers. We have also observed inflection points on the voltage vs. brightness characteristics of the samples, the position of which depends on the frequency of the exciting voltage and the temperature. The observed dependences are explained using concepts describing the mechanisms of pre-breakdown luminescence. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 631–636, September–October, 2006.     

Synthesis and characterization of Mn<Superscript>2+</Superscript>-doped ZnS nanoparticles

Mn²⁺-doped ZnS nanoparticles were prepared by chemical arrested precipitation method. The samples were heated at 300, 500, 700 and 900°C. The average particle size was determined from the X-ray line broadening. Samples were characterized by XRD, FTIR and UV. The composition was verified by EDAX spectrum. The hexagonal structure of the sample was identified. The size of the particles increased as the annealing temperature was increased. The crystallite size varied from 5 nm to 34 nm as the calcination temperature increased. At around 700°C, ZnS is converted into ZnO phase due to oxidation. The emission peak of the sample is observed at 300 nm resulting in blue emission. The solid state theory based on the delocalized electron and hole within the confined volume can explain the blue-shifted optical absorption spectra. UV-VIS spectro-photometric measurement shows an indirect allowed band gap of 3.65 eV.      

Paramagnetic resonance of Mn<Superscript>4+</Superscript> and Mn<Superscript>2+</Superscript> centers in lanthanum gallate single crystals

An increase in the manganese concentration in lanthanum gallate in the range 0.5–5.0% has been found to result in a complete replacement of individual Mn⁴⁺ ions by Mn²⁺ ions. The relative concentrations and binding energies of individual Mn⁴⁺, Mn³⁺, and Mn²⁺ ions have been determined. The spin Hamiltonians of the Mn²⁺ and Mn⁴⁺ centers in the rhombohedral and orthorhombic phases, respectively, have been constructed and the orientation of the principal axes of the fine-structure tensor of Mn⁴⁺ at room temperature has been found. The possibility of using electron paramagnetic resonance for determining the rotation angles of oxygen octahedra of lanthanum gallate with respect to the perovskite structure has been discussed.     

Adiabatic elastic moduli in ZnSe : Mn<Superscript>2+</Superscript> and ZnSe : V<Superscript>2+</Superscript> crystals

The temperature dependences of the elastic moduli C ₄₄ (C ₁₁ ? C ₁₂)/2 and C _l = (C ₁₁ + C ₁₂ + 2C ₄₄)/2 of ZnSe : V²⁺ (impurity concentration, 6 × 10¹⁸ cm^?3) and ZnSe : Mn²⁺ (9.4 × 10²⁰ cm^?3) are measured in the temperature range 1.4–100.0 K at frequencies of 52 and 156 MHz. The temperature dependences of the adiabatic elastic moduli are derived. It is established that softening of the symmetry modules is observed only in the crystal with an impurity having orbitally degenerate states.     

Excitation spectra and structure of luminescence centers of manganese ions in single crystals of zinc sulfide

We investigate the photoluminescence excitation spectra in ZnS:Mn single crystals at room temperature and at the temperature of liquid nitrogen with a different concentration of Mn²⁺ ions. The strongest bands peaking at 557, 578, 600, and 637 nm are associated with a different position of the Mn ion in the lattice of the crystals under investigation. The difference obtained in the excitation spectra can be explained by the resonance transfer of energy between the Mn ions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 208–210, March–April, 2000.     

Effect of isoelectronic impurities K<Superscript>+</Superscript> and I<Superscript>−</Superscript> on luminescence of CsBr:Eu<Superscript>2+</Superscript> crystals

We have investigated the photoluminescence (PL) and photostimulated luminescence (PSL) spectra at 300 K to study the effect of isoelectronic impurities K⁺ and I⁻ on the formation and energy structure of Eu²⁺-V_Cs isolated dipole centers and aggregate centers in the form of single crystals of CsEuBr₃ in CsBr:Eu²⁺ single crystals. We have shown that K⁺ and I⁻ impurities in a concentration of 5 mol% do not have a substantial effect on the energy spectrum of isolated dipole centers in CsBr:Eu²⁺ single crystals and the processes for the formation of such centers during growth of CsBr:Eu single crystals from the melt by the Bridgman method. We have established that in Cs_0.95K^0.05Br:Eu²⁺, more favorable conditions are realized for the formation of aggregate centers than in CsBr:Eu²⁺ and CsBr^0.95K^0.05Br:Eu²⁺ single crystals. So in order to improve the storage properties of phosphors based on CsBr:Eu²⁺, in particular for increasing the efficiency of PSL excitation, it is expedient to dope them with K⁺ impurity in a concentration up to 5 mol%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 627–630, September–October, 2007.     

Temperature quenching of intracenter luminescence of Mn<Superscript>2+</Superscript> ions in diluted magnetic semiconductors

The Spectr-W³ database was developed in 2001–2013 and is available online (http://spectrw3. snz.ru). The database contains information on various spectroscopic constants of atoms and ions such as the wavelengths and probabilities of radiative transitions, energy levels of atoms and ions, ionization potentials, autoionization rates, and the parameters of analytical approximation of cross sections and rates of collisional transitions in atoms and ions. Spectr-W³ presently contains around 450 thousand records and is the world’s largest factual database on spectral properties of multicharged ions. A new stage of development of Spectr-W³, which involves adding a new section titled “Emission Spectrograms” to the database, commenced in 2014. In contrast to the already existing sections that contain tabulated data, this new section provides graphical data (with necessary explanatory notes) on the spectrograms of emission of atoms and ions excited in various plasma sources. The structure of sections of the Spectr-W³ database is characterized, and examples of queries and the corresponding search results are given.     

High-precision mass measurements of hydrogen-like <Superscript>24</Superscript>Mg<Superscript>11+</Superscript> and <Superscript>26</Superscript>Mg<Superscript>11+</Superscript> ions in a Penning trap

For the determination of the bound-electron g factor in hydrogen-like heavy ions the mass of the ion is needed at a relative uncertainty of at least 1 ppb. With the SMILETRAP Penning trap mass spectrometer at the Manne Siegbahn Laboratory in Stockholm several mass measurements of ions with even-even nuclei at this level of precision have been performed so far, exploiting the fact that the mass precision increases linearly with the ion charge. Measurements of masses of the hydrogen-like ions of the two Mg-isotopes ²⁴Mg and ²⁶Mg are reported. The masses of the hydrogen-like ions are 23.979011054(14) u and 25.976562354(34) u, corresponding to the atomic masses 23.985041690(14) u and 25.982592986(34) u, respectively. The possibility to use these two isotopes for the first observation of an isotope effect in the bound-electron g factor in hydrogen-like heavy ions is discussed.     

Theoretical study of charge-exchange and excitation processes in collisions of He<Superscript>+</Superscript> ions with C<Superscript>5+</Superscript>, N<Superscript>6+</Superscript>, and O<Superscript>7+</Superscript> hydrogen-like ions

Data on the cross sections for single-electron charge exchange and excitation in collisions of He⁺ ions with C⁵⁺, N⁶⁺, and O⁷⁺ ions in the He⁺ ion energy range of 0.2–3.0 MeV are obtained for the first time. The cross sections for the single-electron charge transfer into the singlet and triplet 1snl states of C⁴⁺, N⁵⁺, and O⁶⁺ (2≤n≤5) ions and for the 1s → 2p _{0, ±1} electronic excitation of He⁺(1s) ions are calculated. The calculations were performed by solving close-coupling equations on the basis of ten two-electron quasi-molecular states.     

Formation of Eu<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> centers in synthesis of CaF<Subscript>2</Subscript>:Eu luminophores

We have studied the effect of CaF₂:Eu luminophore synthesis methods on the charge state of europium. We have shown that Eu³⁺ predominates over Eu²⁺ in samples obtained by coprecipitation of europium with calcium fluoride, and the ratio Eu³⁺/Eu²⁺ grows as the total amount of europium increases. Partial charge conversion of the europium occurs during calcination of the samples, due to changes in the excess fluorine balance. We studied the luminescence, magnetic susceptibility, and EPR of the synthesized samples. We have shown that in a solid solution, europium forms large ordered clusters, determining both the luminescent and the magnetic properties of the material. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 773–779, November–December, 2007.     

Photodynamic processes in CaF<Subscript>2</Subscript> crystals activated by Ce<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

The photochemical properties of CaF₂ crystals activated by Ce³⁺ and Yb³⁺ ions are studied. A model of the photodynamic processes induced by pumping UV or VUV radiation in active media is suggested and experimentally verified. This model explains both the presence of color centers of electronic and hole nature in crystals activated by cerium and the mechanism of suppressing of solarization processes after additional activation of the samples by Yb³⁺ ions. The cross sections of the processes of free-carrier capture by various ytterbium impurity centers are estimated. These impurity centers are established to be effective centers of recombination of free carriers of both signs.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Migration of Mn<Superscript>2+</Superscript> excitations in Cd<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>Te crystal

The experimentally obtained intensity decay curves for the 2-eV intracenter luminescence band of Mn²⁺ ions in Cd_0.5Mn_0.5Te semiconductor solid solution at a temperature of 77 K have been simulated by the Monte Carlo method. The calculations show that the initial nonexponential behavior of the intensity decay curves at the band wings, as well as the time dependence of the band peak energy, are determined by the fast migration of excitations through the Mn²⁺ ion subsystem. There are more than 200 jumps per each emitted photon, and the migration rate increases by almost two orders of magnitude in comparison with the rate at 4 K. The analysis of the simulation results and the calculation based on the experimental data show the interaction between ions to be resonant. The estimate derived from the Anderson criterion suggests that the excited state is not delocalized. An increase in the migration rate with an increase in temperature significantly reduces the inhomogeneous broadening dispersion.     

H<Superscript>+</Superscript><Emphasis Type="Bold">and He</Emphasis><Superscript>2+</Superscript> impact single and double ionization of lead

H⁺ and He²⁺ impact single and double ionization cross sections of ground state lead atoms have been calculated in the binary encounter approximation. Calculations of direct double ionization cross sections have been performed in the modified double binary encounter model. The accurate expressions of σ_ΔE (cross-section for energy transfer ΔE) and Hartree-Fock velocity distributions for the target electrons have been used throughout the calculations. Contributions to double ionization from Auger effect following ionization of inner shells have been considered in the present work. Our H⁺ impact single and double ionization cross sections are in good agreement with the experimental observations. In calculations of He²⁺ impact cross sections, the present theoretical approach shows limited success in the experimentally investigated region (50–350 keV amu^-1).     

Concentration dependence of the quantum yield of luminescence of Tm<Superscript>3+</Superscript> ions in gadolinium oxychloride

The concentration dependence of the quantum yield of luminescence of Tm³⁺ ions in an oxychloride matrix has been measured in individual bands of their luminescence excited at different wavelengths. The concentration dependences of the quantum yield of luminescence were calculated with allowance for the effect of the unintentional impurity of rare-earth ions. The cross-relaxation nature of the concentration dependence of the rare-earth ion luminescence is discussed.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 759–765, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Defect Structure and Up-conversion Luminescence Properties of ZrO<Subscript>2</Subscript>:Yb<Superscript>3+</Superscript>,Er<Superscript>3+</Superscript> Nanomaterials

The up-converting ZrO₂:Yb³⁺,Er³⁺ nanomaterials were prepared with the combustion and sol–gel methods. FT-IR spectroscopy was used for analyzing the impurities. The crystal structures were characterized with X-ray powder diffraction and the mean crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence measurements were made at room temperature with IR-laser excitation at 977 nm. The IR spectra revealed the conventional and OH⁻ impurities for the combustion synthesis products. The structure of the ZrO₂:Yb³⁺, Er³⁺ nanomaterials was cubic except for the minor monoclinic and tetragonal impurities obtained with the sol–gel method. The materials showed red (650–700 nm) and green (520–560 nm) up-conversion luminescence due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. The products obtained with the combustion synthesis exhibited the most intense luminescence intensity and showed considerable afterglow.     

Online diagnosis of electron excitation temperature in CH<Subscript>4</Subscript>+H<Subscript>2</Subscript> discharge plasma at atmospheric pressure by optical emission spectra

Methane coupling under low temperature plasmas at atmospheric pressure is a green process by use of renewable sources of energy. In this study, CH₄+H₂ discharge plasma was on-line diagnosed by optical emission spectra so as to characterize the discharge system and to do spade work for the optimization of the technical parameters for future commercial production of methane coupling under plasmas. The study was focused on a calculation method for the online diagnosis of the electron excitation temperature in CH₄+H₂ discharge plasma at atmospheric pressure. The diagnostic method is easy, efficient and fairly precise. A serious error in a literature was corrected during the reasoning of its series of equations formerly used to calculate electron temperatures in plasmas. Supported by the National Natural Science Foundation of China (Grant Nos. 29776037 and 10675028) and the Science and Technology Development Foundation of SINOPEC (Grant No. X500005)     

Electron paramagnetic resonance of Mn<Superscript>2+</Superscript> ions in single crystals of yttrium aluminum borate YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are studied using electron paramagnetic resonance spectroscopy. It is shown that manganese ions introduced at low concentrations into the sample predominantly occupy yttrium ion sites in the crystal structure. The shape of the electron paramagnetic resonance spectrum unambiguously indicates that the valence of manganese ions in this case is equal to 2+. The parameters of the spin Hamiltonian of Mn²⁺ ions in the YAl₃(BO₃)₄ matrix are determined at room temperature. The magnitude and sign of the fine structure parameter D allow the conclusion that the YAl₃(BO₃)₄ single crystals doped with manganese ions have a strong crystal field at the yttrium ion sites and easy-axis anisotropy.     

Submillimeter ESR spectra of Fe<Superscript>2+</Superscript> ions in synthetic and natural beryl crystals

Electron spin resonance spectra of non-Kramers bivalent iron (Fe²⁺) ions have been detected in synthetic and natural beryl crystals with an iron impurity. The observed ESR spectra have been attributed to resonance transitions of Fe²⁺ ions from the ground (singlet) state to excited (doublet) levels with the splitting Δ = 12.7 cm^–1 between the levels. The experimental angular and frequency dependences of the resonance field of the ESR signal have been described by the spin Hamiltonian with the effective spin S = 1. The analysis of the ESR data and optical absorption spectra indicates that the Fe²⁺ ions are situated in tetrahedral positions and substitute Be²⁺ cations in the beryl structure.