Photoionization spectra of silver dimers adsorbed on the surface of a ZnS single crystal

We use the photostimulated luminescence flash method to measure photoionization spectra of Ag₂ clusters adsorbed on the surface of a ZnS single crystal. Adsorbed dimers of silver are prepared by treatment of the surface of a ZnS single crystal in high vacuum with a beam of molecular Ag ₂ ⁺ ions followed by their neutralization. We show that the adsorbed dimers create two types of electron traps at energy levels 1.63 and 1.82 eV below the bottom of the conduction band. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 545–547, July–August, 2007.     

Anti-stokes luminescence of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed organic dye molecules and few-atom silver clusters

For microcrystals of Zn_0.6Cd_0.4S with adsorbed molecules of a number of organic dyes, we have observed sensitized anti-Stokes luminescence excited by radiation with wavelengths in the range 610–750 nm and flux density 10¹⁴–10¹⁵ photons/cm²·sec. The positions of the bands in the excitation spectra for such luminescence match those of the absorption spectra for the adsorbed dye molecules, which is evidence in favor of a cooperative mechanism for its appearance. We have shown that enhancement of the anti-Stokes luminescence is possible when silver atoms and few-atom clusters appear on the Zn_0.6Cd_0.4S surface in addition to the dye molecules. We hypothesize that its excitation in the latter case occurs as a result of two-photon optical transitions. These transitions occur sequentially, with transfer of an electron or the electronic excitation energy from the dye molecules to silver atoms and few-atom clusters adsorbed on the surface of Zn_0.6Cd_0.4S, creating deep localized states in the bandgap with photoionization energies 1.80–2.00 eV. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 617–621, September–October, 2007.     

Sensitized anti-Stokes luminescence centers in microcrystals of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed dye molecules and few-atomic silver clusters

The sensitized anti-Stokes luminescence excited by radiation with wavelengths from 610 to 750 nm and flux densities of 10¹⁴–10¹⁵ quanta/(cm²·s) is detected for microcrystals of Zn _0.6 Cd _0.4 S solid solutions with adsorbed organic malachite green and methylene blue dye molecules. The position of its excitation spectra coincides with that of the absorption spectra of adsorbed dye molecules, which suggests the cooperative mechanism of its occurrence. The possibility of amplification of the anti-Stokes luminescence by means of adsorption of silver atoms and few-atomic silver clusters, in addition to the dye molecules, on the Zn _0.6 Cd _0.4 S surface is investigated. It is assumed that in the latter case, the anti-Stokes luminescence is excited as a result of two-quantum optical transitions with electron or electron excitation energy transfer from the dye molecules adsorbed on the Zn _0.6 Cd _0.4 S surface to silver atoms and few-atomic silver clusters creating deep local states with photoionization energies of 1.8–2.0 eV in the gap. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 21–26, March, 2008.     

Stimulation of secondary negative ion emission by implantation of alkaline ions into the surface layer of a solid followed by heating

A new method of stimulating secondary negative ion emission is suggested that is based on implantation of alkaline ions into the surface layer of a solid with subsequent heating to a temperature providing optimal coverage of the surface (about half a monolayer) by activator (alkaline) ions. It is shown that, by appropriately selecting the implantation dose (10¹⁸–10¹⁹ cm⁻³) and surface temperature (500–900°C), one can reach such a degree of coverage of the sample surface by activator ions that its work function eφ becomes minimal: 1.9 eV for molybdenum and 2.1 eV for copper. It is found that, with the implantation (irradiation) dose and surface temperature chosen properly, one can, by means of outdiffusion of cesium atoms, achieve such a degree of surface coverage that remains unchanged during the continuous sputtering of the surface by a cesium ion beam.     

Entrapment of inert gas ions near molybdenum surface

The thermal desorption spectra of inert gas ions (neon, argon and krypton) injected with various energies (430–1950 eV) into a polycrystalline molybdenum target with various dosages (6.4×10¹²−3.9×10¹⁴ ions/cm²) are reported. At least four different states of binding of the trapped atoms corresponding to the activation energies for desorption have been observed from the spectra. The activation energies are found to be relatively insensitive to the species of the bombarding ion, incident ion energy and the dosage. The shapes of the spectra are strongly influenced by the depth of penetration of the ions into the solid. The activation energies deduced are in good agreement with those reported for the migration of atoms and defects in molybdenum.     

Latex-mediated synthesis of ZnS nanoparticles: green synthesis approach

A low-cost, green synthesis of ZnS nanoparticles is reported using 0.3 % latex solution prepared from Jatropha curcas L. ZnS nanoparticles were characterized by X-ray diffraction, selected area electron diffraction, transmission electron microscopy, energy dispersive analysis of X-rays, UV–vis optical absorption and photoluminescence techniques. Fourier Transform Infrared Spectroscopy was performed to find the role of cyclic peptides namely curcacycline A (an octapeptide), curcacycline B (a nonapeptide) and curcain (an enzyme) as a possible reducing and stabilizing agents present in the latex of J. curcas L. The average size of ZnS nanoparticles was found to be 10 nm. Latex of J. curcas L. itself acts as a source of sulphide (S⁻²) ions that are donated to Zn ions under present experimental conditions. Source of sulphide (S⁻²) ions is still unclear, but we speculate that cysteine or thiol residues present in enzyme curcain may be donating these sulphide (S⁻²) ions.     

Mechanism of photoluminescence excitation of Mn<Superscript>2+</Superscript> ions in ZnS crystals

The mechanisms of photoluminescence excitation of Mn²⁺ ions in ZnS crystals have been investigated on the basis of complex analysis of the temperature dependences of the photoluminescence and photoluminescence-excitation spectra of ZnS:Mn crystals. The activation energy of a manganese luminescence center was estimated at E_a = 0.17 ± 0.05 eV. It is shown that E_a represents an energy band with a width ΔE_a = 0.1 eV, within which a manganese luminescence center can experience radiationless recombination. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 788–793, November–December, 2005.     

Formation of excited states of atoms and ions in laser plasma from CuInS2

Emission spectra and the energy distribution of the excited-state population density of atoms and ions in erosion laser plasma from CuInS₂ with various crystal-structure orderings are analyzed. It is shown that increased ordering of the target crystal structure causes the excited-state energies of indium atoms generated in the laser erosion plume to increase and that sulfur atoms always emit only in transitions from highly excited states. The ratio of relative ion concentrations in the laser plasma plume is Cu⁺/In⁺/S⁺ = 0.3/0.08/2, which corresponds neither to the atomic ratio of Cu/In/S (1/1/2) in the target nor to the ratio of ionization energies. The results are explained by recombination processes for ions and by the atomization specifics of the CuInS₂ target exposed to long-wavelength radiation. The atomization consists essentially of dissociative processes expressed by CuInS₂ → CuInS + S and CuInS₂ → Cu + InS + S. The electron temperature of polycrystal (single-crystal) plasma at a distance of 1 mm from the target is 0.3 eV (0.4 eV) for atoms and 1.3 eV (2.7 eV) for ions and varies negligibly for plasma up to a distance of 7 mm from the target. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 217–223, March–April, 2008.     

Pulsed cathodoluminescence of feldspars

We have studied the spectral and kinetic characteristics of pulsed cathodoluminescence of feldspars (albite, microcline, amazonite) in the time range 10⁻⁸–10⁻² sec and the temperature range 28–300 K. We have shown that the bands in the UV region of the spectrum (5.39, 4.35, and 3.75 eV) are due to intrinsic luminescence of the crystals. The ratio of the intensities of these bands characterizes the phase composition of the mineral: in the luminescence spectra of microcline, for all temperatures the 4.35 eV band dominates; in the pulsed cathodoluminescence spectra of albite, the bands at 3.75 eV (at 300 K) and 5.39 eV (at 28 K) dominate. The parameters of the luminescence decay kinetics for the impurity ions Fe³⁺ and Mn²⁺ are more sensitive to local perturbations of the lattice structure than the position of the emission band maximum, and can be an effective indicator of the origin of the mineral. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 339–343, May–June, 2006.     

Quasi-ordered nanostructures on the surface of strontium titanate

The results of the investigation of the surface of strontium titanate single crystals after treatment with high-energy plasma are presented. The surface morphology of the strontium titanate single crystals and the change in its characteristics after plasma treatment have been studied using electron scanning and atomicforce microscopy. A change in the electronic state of a part of the titanium ions and a change in the stoichiometry in the modified near-surface layer have been found by the method of valence shift of X-ray lines. A preliminary analysis has been made of the conditions providing the formation of single- and two-level systems of ordered crystallites with sizes of 10⁻⁷–10⁻¹⁰ m on the surface of single-crystal strontium titanate with impurities of ions of the iron and lanthanum groups.     

Secondary ion emission from bismuth under bombardment with Bi m ? and Au m ? cluster ions

The mass spectra of secondary cluster ions Bi _n ⁺ (n = 1–9) from bismuth sputtered by (6–21) keV Au _m ⁻ (m = 1–9) and Bi _m ⁻ (m = 1–5) cluster ions have been investigated. New features of manifestation of dense nonlinear cascades and thermal spikes have been revealed. It is concluded that the thermal spike regime makes a significant contribution to the mechanism of formation of small cluster ions, containing up to seven atoms for a bismuth target.     

The evolution of roughness of supersmooth surfaces by ion-beam etching

The behavior of roughness on surfaces of Cr/Sc multilayer structure, crystalline silicon [100], and fused quartz upon ion beam etching in the region of middle and high frequencies of the spatial spectrum (10⁻²–10² μm⁻¹) is studied. The possibility of keeping surface roughness at level σ ∼ 0.3 nm upon etching by Ar atoms/ions to depths of up to 10 μm is demonstrated.     

Thermoluminescence in single crystals of RbBr:OH− and RbBr:Ca2+

Optical absorption, thermoluminescence glow and emission spectra of RbBr:Ca²⁺ and RbBr:OH⁻ have been studied and analysed. It is observed that both Ca²⁺ and OH⁻ ions enhance theF-centre concentration.F _Z1 band in RbBr:Ca²⁺ appears at 1.55 eV. TL glow peak corresponding toF _Z1 centre on analysis gives a trap depth of 0.84 eV. OH⁻ ions in the crystal seem to act as TL ‘killers’. Spectral distribution of emission under the glow peaks shows five bands around 1.5, 1.8, 2.1, 2.5 and 2.9 eV. Probable models of TL mechanism are suggested to explain the observed TL emission bands.     

Muon/muonium surface interactions

The interactions of muonium (μ ⁺ e ⁻, Mu) with the surfaces of fine silica powders have been extensively studied using zero, longitudinal and transverse field μSR techniques. These studies indicate diffusion and trapping behavior of the Mu atoms on the silica surface, which is strongly influenced by the surface hydroxyl (OH) concentration. Specifically, the presence of the surface OH groups is observed to inhibit the surface mobility of the Mu atoms at low temperatures. Information provided by zero and longitudinal field data suggest a random anisotropic distortion of the Mu hyperfine interaction (RAHD) as the principal relaxation mechanism. A recently developed RAHD spin relaxation theory is used to interpret these data. Additional investigations, using platinum loaded silica, have yielded the first observed surface reaction of Mu. Studies of the interactions of positive muons with surfaces have been also extended to single crystals, where low energy (<10 eV)μ ⁺ andMu ⁻ ions are observed to be reemitted from some materials (e.g., the <100> surface of lithium fluoride). Future applications of these emission phenomena toward the development of a slow^847-3 (or Mu⁻) beam are considered.     

UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Time-resolved spectroscopy of natural and synthetic BeO crystals

The results of comparative luminescence investigation of natural and synthetic BeO crystals are presented. Time-resolved luminescence (2.5–8 eV) and luminescence excitation spectra, and the kinetics of glow decay were measured using ultraviolet-vacuum-ultraviolet (VUV) synchrotron radiation (5–22 eV) or x-radiation (50–620 eV or 3–62 keV) ranges. X-ray and thermostimulated luminescence of natural BeO crystals were compared to the glow of additively colored synthetic crystals. The characteristic luminescence of F and F ⁺ centers was found in natural crystals. In synthetic crystals similar luminescence is observed only after additive or radiation coloration by virtue of the creation of F ⁻ and F ⁺ centers on anion vacancies. The defects found in the crystal lattice of a natural BeO crystal testify to the degree of mineral metamictization of the given deposit.     

Modeling the atomic and electronic structure of diamond nanocrystals containing [NV]<Superscript>−</Superscript> centers by the density functional method

We have used the density functional method to model the atomic and electronic structure of diamond nanocrystals passivated by hydrogen atoms and either not containing defects or containing a single [NV]⁻ center. We have shown that in all cases, after relaxation the nanocrystals are formed as diamond-like structures. We have studied the features of the electronic structure of the nanocrystals. We have analyzed in detail the mechanism for the formation of energy levels in the bandgap due to [NV]⁻ centers. We have established that the optical absorption and fluorescence spectra for the [NV]⁻ centers are mainly associated with transitions of electrons between the highest occupied β orbitals (projection of the electron spin equal to +1/2) and lower unoccupied α orbitals (projection of the electron spin equal to −1/2). The results on the localization and energy position of the states in the bandgap match data obtained for the [NV]⁻ center in bulk diamond. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 86–92, January–February, 2007.     

Relaxation of electronically excited products of solid-state reactions in the crystal lattice

The mechanisms of deactivation of electronically excited products of decomposition of silver azide (nitrogen molecules) are examined. A model of dipole interaction with the electron subsystem of the crystal is used to estimate the rate constants of deactivation with formation of electron-hole pairs (∼10⁹ s⁻¹) and energy transfer to a band hole (∼10⁻¹² cm³ s⁻¹). The values obtained confirm the basic postulate underlying the models of solid-phase chain reactions: the preferential formation of electronic excitations of the crystal lattice during the deactivation of excited decomposition products.     

Electronic and optical properties of Ho-doped BYF crystal

First-principles methods have been applied to explore the electronic and optical properties of BYF single crystals heavily doped with the Ho³⁺ ion (16.33 and 30.36 mol%). The electronic properties calculations manifest that the top of the valence band is dominated by 2p-orbitals of the F atoms and 4f-orbitals of the Ho atoms. The new defect states are dominated by 4f-orbitals of the Ho atoms which exist in the forbidden band. The principal absorptionat around 5.13 eV (241.7 nm) and 5.75 eV (215.7 nm) occurs in ultra-violet range owing to the electronic transitions from the occupied 2p-orbitalsof the F atoms as well as 4f-orbitals of the Ho atoms to empty 4f-orbitals of neighboring Ho atoms. Moreover, the influence of crystal field will split the energy levels of rare earth ions and easily release the parity forbidden condition of free rare earth ions resulting in f-f transition. Therefore, there may be a 2 μm luminescence in the Ho-doped BYF crystal.