X-ray emission and photoluminescence spectroscopy of nanostructured silica with implanted copper ions

Quartz glass samples and compacted SiO₂ nanopowders have been studied by x-ray emission (CuL _{2, 3} transition 3d4s → 2p _{1/2, 3/2}) and photoluminescence spectroscopy following pulsed Cu⁺ ion implantation (energy, 30 keV; pulse current up to 0.5 A; pulse duration, 400 μs; irradiation doses, 10¹⁵, 10¹⁶, and 2 × 10¹⁷ cm^?2). It has been established that ion irradiation gives rise to the formation of glassy and compacted SiO₂ samples of nanosized metallic and oxide phases in the structure. An analysis of CuL x-ray emission spectra has shown that copper nanoparticles are thermodynamically metastable and chemically active because ion beam bombardment transfers them readily to the oxide form. This results from the radiation-stimulated fracture of regular Si-O-Si bonds in amorphous SiO₂ and the formation of defective Si-Si bonds, followed by capture of oxygen by copper atoms. The enhanced degree of oxidation of copper ions in SiO₂ nanostructured pellets can be reduced by coimplantation and thermal annealing. Optical spectroscopy studies suggest that, in glasses and SiO₂ nanostructured pellets, there exist metallic Cu _n ⁰ nanoclusters, which at low temperatures exhibit quantum-confined photoluminescence with a characteristic stepped excitation spectrum.     

Energy band structure and X-ray spectra of phenakite Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

The electronic structure of crystalline phenakite Be₂SiO₄ is investigated using x-ray emission spectroscopy (XES) (Be K _α XES, Si L _{2, 3} XES, O K _α XES) and x-ray absorption spectroscopy (XAS) (Be 1s XAS, Si 2p XAS, O 1s XAS). The energy band structure is calculated by the ab initio full-potential linearized augmented-plane-wave (FLAPW) method. The total and partial densities of states and the dispersion curves for the Be₂SiO₄ compound are presented. It is shown that the top of the valence band and the bottom of the conduction band of the Be₂SiO₄ compound are predominantly formed by the oxygen 2p states. According to the results obtained, the electron transition with the lowest energy supposedly can occur at the center of the Brillouin zone. The effective masses of electrons (0.5m _e ) and holes (3.0m _e ) for the Be₂SiO₄) compound are estimated.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

Effect of laser irradiation on the structure and valence states of copper in Cu-phosphate glass by XPS studies

The effect of laser irradiation using three different wavelengths (IR, visible and UV) generated from Nd:YAG laser on the local glass structure as well as on the valence state of the copper ions in copper phosphate glass containing CuO with the nominal composition 0.30(CuO)-(0.70)(P₂O₅), has been investigated by X-ray photoelectron spectroscopy (XPS). The presence of asymmetry and satellite peaks in the Cu 2p spectrum for the unirradiated sample is an indication of the presence of two different valence states, Cu²⁺ and Cu⁺. Hence, the Cu 2p_3/2 spectrum was fitted to two Gaussian-Lorentzian peaks and the corresponding ratio, Cu²⁺/Cu_total, determined from these relative areas clearly shows that copper ions exist predominately (>86%) in the Cu²⁺ state for the unirradiated glass sample under investigation. For the irradiated samples the symmetry and the absence of satellite peaks in the Cu 2p spectra indicate the existence of the copper ions mostly in Cu⁺ state. The O 1s spectra show slight asymmetry for the irradiated as well as unirradiated glass samples which result from two contributions, one from the presence of oxygen atoms in the P-O-P environment (bridging oxygen BO) and the other from oxygen in an P-O-Cu and PO environment (non-bridging oxygen NBO). The ratio of NBO to total oxygen was found to increase with laser power.     

Local electronic structure of Cu2O,CuO and YBa2Cu3O7−δ

Cu 3d and O 2p electronic states of Cu₂O, CuO, and the highT _c compound YBa₂Cu₃O_7– have been probed by means of high resolution x-ray emission spectroscopy (XES). The CuL and OK XES bands are compared in detail with recently reported x-ray photoelectron and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements and densities of states obtained by local density functional (LDF) theory. The XES data show that the hybridization between Cu 3d and O 2p states is completely modified in CuO and YBa₂Cu₃O_7–, whered-d correlation energy is large, as compared to LDF predictions. Such is not the case for Cu₂O where agreement between theory and experiment is good.The Cu 3d states are found to be highly localized in YBa₂Cu₃O_7– (though less so than in CuO). The O 2p states lie at lower binding energies than in the simpler oxides and are mainly situated above the Cu 3d states. The respective positions of the centre of gravity of the OK emission bands on an x-ray energy scale indicate that the oxygen sites are less well screened by the O 2p states in the highT _c compound. This provides indirect evidence for the presence ofd-like states at the oxygen sites.     

High-performance hierarchical cypress-like CuO/Cu<Subscript>2</Subscript>O/Cu anode for lithium ion battery

Composite CuO/Cu₂O/Cu anode for lithium ion battery was designed and synthesized via facile electrodeposition and the subsequent in situ thermal oxidation in air at 300 °C for 1 h. The as-prepared composite CuO/Cu₂O/Cu anode was studied in terms of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), galvanostatic charge/discharge, cyclic voltammetry (CV), and AC impedance. As expected, the composite CuO/Cu₂O/Cu with CuO-rich surface displayed hierarchical cypress-like morphology; furthermore, the hierarchical cypress-like CuO/Cu₂O/Cu anode also delivered satisfactory electrochemical performances. For example, the reversible discharge capacity remained at 534.1 mAh/g even after 100 cycles. The enhanced electrochemical performances were attributed to the hierarchical cypress-like porous structure and the synergistic effect among the composite active copper oxides and highly conductive Cu current collector.     

Pressure-induced electron spin transition in the paramagnetic phase of the GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Heisenberg magnet

The HS → LS spin crossover effect (high-spin → low-spin transition) induced by high pressure in the range 45–53 GPa is observed in trivalent Fe³⁺ ions in the paramagnetic phase of a Gd⁵⁷Fe₃(BO₃)₄ gadolinium iron borate crystal. This effect is studied in high-pressure diamond-anvil cells by two experimental methods using synchrotron radiation: nuclear resonant forward scattering (NFS) and Fe K _β high-resolution x-ray emission spectroscopy (XES). The manifestation of the crossover in the paramagnetic phase, which has no order parameter to distinguish between the HS and LS states, correlates with the optical-gap jump and with the insulator-semiconductor transition in the crystal. Based on a theoretical many-electron model, an explanation of this effect at high pressures is proposed.     

Influence of Bi<Superscript>3+</Superscript> ions on low temperature D.C. conductivity of Na<Subscript>2</Subscript>SiCuO<Subscript>4</Subscript> glasses

Sodium silicate glasses doped with CuO and mixed with different contents of Bi₂O₃ (ranging from 4 to 16 mol%) were prepared. D.C. conductivity studies over a range of temperature from 225 to 325 K have been carried out. The conductivity is observed to decrease linearly with increase of Bi₂O₃ concentration. The results are analyzed using optical absorption, ESR, and IR spectral data. The spectroscopic studies have indicated that there is a gradual reduction divalent copper ions to monovalent ions with increase of Bi₂O₃ concentration. These studies have also indicated that such Cu⁺ ions participate in the glasses network forming and increase the polymerization of the glass network. The analysis of the results of D.C. conductivity indicated that in temperature region T > θ _D/2, the small polaron hoping model is valid, and the conduction is predicted to be adiabatic type. The analysis of the results has further revealed that there is a gradual change over of conduction mechanism from ionic to electronic with increase of Bi₂O₃ concentration. The low temperature part of D.C. conductivity is explained using variable range hopping (VRH) model.     

Diamagnetic nuclear <Superscript>119</Superscript>Sn probes in the copper chromites CuCr<Subscript>2</Subscript>X<Subscript>4</Subscript> (X = O,S, Se) with a spinel structure

The CuCr₂X₄ (X = O, S, Se) spinel system has been studied by the Mössbauer spectroscopy of the nuclear diamagnetic ¹¹⁹Sn probe at low temperatures in an external magnetic field. The hyperfine magnetic fields H ^Sn induced by paramagnetic ions at tin nuclei in the CuCr₂S₄ and CuCr₂Se₄ chalcogenides have giant values and are somewhat higher than those detected in the CuCr₂O₄ oxide. This behavior is caused by the strong covalence of the chalcogenides, which is supported by the experimentally found isomer shifts. The H ^Sn field is found to be mainly contributed by superexchange 90° interactions in the B-sublattice along the Cr[B]-X-Sn[B] bond chain, whose role increases in the series O-S-Se. In the oxygen CuCr₂O₄ spinel, the partial contributions to the H ^Sn field induced by the Cu²⁺ and Cr³⁺ ions are estimated. The local magnetic structure of the CuCr₂O₄ spinel is refined, and its total magnetization is shown to be directed along the magnetic moment of copper in the A sublattice.     

Hyperfine nuclear interaction at copper lattice sites of high-temperature superconductors studied by <Superscript>61</Superscript>Cu(<Superscript>61</Superscript>Ni) Mössbauer emission spectroscopy

Mössbauer emission spectroscopy on the ⁶¹Cu(⁶¹Ni) isotope has been used to determine the quadrupole coupling constant C(Ni) and magnetic induction B(Ni) for the ⁶¹Ni²⁺ probe at copper sites in Cu₂O, CuO, La_{2 ?x}Ba_xCuO₄, Nd_2?xCe_xCuO₄, RBa₂Cu₃O₆, and RBa₂Cu₃O₇ (R=Y, Nd, Gd, Yb). The compounds containing divalent copper were found to exhibit linear C(Ni) vs. C(Cu) and B(Ni) vs. B(Cu) relations [C(Cu) and B(Cu) are the quadrupole coupling constant and magnetic induction for the ⁶³Cu probe, respectively, found by NMR], which is interpreted as an argument for the copper being in divalent state. The deviation of the data points corresponding to the Cu(1) sites in RBa₂Cu₃O₆ and RBa₂Cu₃O₇ from the C(Ni) vs. C(Cu) straight line may be due either to the copper valence being other than 2+ (in the RBa₂Cu₃O₆ compounds) or to the principal axes of the total and valence electric field gradient being differently oriented (in the RBa₂Cu₃O₇ compounds).     

Structural,magnetic and optical properties of diluted magnetic semiconductor (DMS) phase of Ni modified CuO nanoparticles

Control on the size of copper oxide (CuO) in the nano range is a highly motivating approach to study its multifunctional nature. The present investigation reports a sol-gel derived Ni doped CuO nanoparticles (Cu_1-xNi_xO). Rietveld refinement of the XRD spectra confirms the formation of single monoclinic phase of Cu_1-xNi_xO nanoparticles having crystallite size within the range of 19–21 nm. Raman spectra show the presence of characteristics Raman active modes and vibrational bands in the Cu_1-xNi_xO samples that corroborate the monoclinic phase of the samples as revealed by refinement of XRD data. The estimated band gap of pure CuO is found to be ∼1.43 eV, which decreases with the increase of dopant concentration into CuO matrix. This result is in line with estimated crystallite size. Magnetization curves confirm the weak ferromagnetic nature of Cu_1-xNi_xO nanoparticles which reveal the DMS phase. This weak magnetic nature may be induced in the samples due to the exchange interaction between the localized magnetic d-spins of Ni ions and carriers (holes or electrons) from the valence band of pristine CuO lattice. Replacement of Cu⁺² by Ni⁺² ions into the host CuO lattice induces the magnetization. The quantified value of squareness ratio (S < 0.5) confirms the inter-grain magnetic interactions in the Cu_1-xNi_xO nanoparticles which is also the reason of weak induced magnetization.     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Nitrogen-doped carbon dots embedded in a SiO<Subscript>2</Subscript> monolith for solid-state fluorescent detection of Cu<Superscript>2+</Superscript> ions

We describe the simple fabrication of SiO₂ sol-gel monoliths embedding highly luminescent carbon nanodots (CDs) sensitive to metal ions. The pristine CDs we synthesize display an intense dual emission consisting in two fluorescence bands in the green and violet region, and we demonstrate that this photoluminescence is substantially unchanged when the dots are incorporated in the SiO₂ matrix. The emission of these CDs is quenched by interactions with Cu²⁺ ions, which can be used to detect these ions with a detection limit of 1 μM. The chromophores remain accessible to diffusing Cu²⁺ ions even after embedding CDs in the sol-gel monolith, where their detection capabilities are preserved. Such a result provides the proof-of-principle of a new sensing scheme, where CDs are exploited as active sensing centers of metal transition ions within a solid-state device. The different interaction mechanisms of CDs with copper, in liquid and solid phase, are analyzed in detail and discussed in terms of different accessibility of their chromophores when the dots are incorporated in the SiO₂ matrix.     

Study of the formation and unimolecular fragmentation of Si<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>O<Stack><Subscript><Emphasis Type="Italic">m</Emphasis></Subscript><Superscript>+</Superscript></Stack> clusters under ion bombardment

The dependences of the emission and fragmentation of clusters sputtered by Xe⁺ ions from the surface of Si _n O _m ⁺ on the oxygen pressure near the bombarded surface are studied using secondary ion mass spectrometry. It is shown that the process of Si _n O _m ⁺ cluster formation under ion bombardment can be described within the framework of the mechanism of combinatorial synthesis by taking into account the mutual reversibility of the reactions of formation and unimolecular decay.     

Secondary ion emission from a GaAs single crystal upon bombardment with Bi<Stack> <Subscript> <Emphasis Type="Italic">m</Emphasis> </Subscript> <Superscript>+</Superscript> </Stack> cluster ions

Secondary-ion mass spectra and energy distributions upon bombarding a gallium arsenide single crystal using Bi_m⁺(m = 1–5) cluster ions with energies of 2–12 keV are investigated. The gallium cluster ion yield grew nonadditively with the number of atoms in the cluster projectiles. A quasi-thermal component found in the energy spectra of secondary Ga⁺ and Ga₂⁺ ions is indicative of the occurrence of the thermal spike mode upon cluster ion bombardment. The quasi-thermal component in the yield of atomic Ga⁺ ions upon bombardment with Bi₂⁺–Bi₅⁺–ions is 35–75%.     

Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering

Microcrystalline cellulose is a porous natural material which can be used both as a support for nanoparticles and as a reducer of metal ions. Cellulose supported nanoparticles can act as catalysts in many reactions. Cu, CuO, and Cu₂O particles were prepared in microcrystalline cellulose by adding a solution of copper salt to the insoluble cellulose matrix and by reducing the copper ions with several reducers. The porous nanocomposites were studied using anomalous small angle X-ray scattering (ASAXS), X-ray absorption spectroscopy, and X-ray diffraction. Reduction of Cu²⁺ with cellulose in ammonium hydrate medium yielded crystalline CuO nanoparticles and the crystallite size was about 6–20 nm irrespective of the copper concentration. The size distribution of the CuO particles was determined with ASAXS measurements and coincided with the crystallite sizes. Using sodium borohydrate or hydrazine sulfate as a reducer both metallic Cu and Cu₂O nanoparticles were obtained and the crystallite size and the oxidation state depended on the amount of reducer.     

Relation between 2p X-ray photoelectron and Kα X-ray emission spectra of manganese and iron oxides

The high resolution Mn and Fe Kα X-ray emission spectra (XES), and Mn and Fe 2p X-ray photoelectron spectra (XPS) for manganese and iron oxides were measured. The spectra were compared with those of [MnO₄]⁻, [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ ions. As the electronic structure of the latter compounds do not change with electron hole creation in the core levels, satellite peaks due to charge transfer are not observed in the 2p XPS spectra, and the peak profiles of metal 2p XPS and Kα XES are governed by the exchange splitting between 2p and valence electrons. The metal 2p XPS spectra of the oxides had satellite peaks, but the XES spectra had no satellites. FWHMs of the metal 2p_3/2 main peaks of the compounds being low spin states are smaller than those of metal Kα₁ XES spectra. However, FWHMs of Mn 2p_3/2 of the manganese oxide were nearly equal to those of Mn Kα₁ XES spectra, and those of Fe 2p_3/2 XPS spectra of the iron oxides are greater than those of Fe Kα₁ XES spectra.     

X-ray emission and X-ray photoelectron spectroscopic studies of fullerene fluoride C<Subscript>60</Subscript>F<Subscript>24</Subscript>

The structure of the fullerence fluoride C₆₀F₂₄ of the T _h symmetry contains two types of chemically different carbon atoms, namely, atoms of isolated double bonds and atoms of CF groups. X-ray photoelectron and x-ray emission spectroscopic studies of C₆₀F₂₄ revealed a difference in the widths of the x-ray bands corresponding to these types of atoms. Nonempirical quantum-chemical calculations performed for C₅₉NF ₂₄ ⁺ ions with a hole in the C 1s core level of the fullerence fluoride showed that the difference in the bandwidths may be due to the fact that the vibrational states of the system are different when 1s electrons are removed from chemically nonequivalent atoms.     

Paramagnetism in copper monoxide systems

This paper describes the problem of high-temperature superconductivity related to investigations of the magnetic susceptibility, electron paramagnetic resonance, and O Kα x-ray emission spectra of samples from the following systems based on copper monoxide: CuO-Cu, CuO-Cu₂O and CuO-MgO. In all these systems, thermal processing results in a paramagnetism which is not observed in the individual components of these systems before they are processed. O Kα spectra of the interface of a Cu-single-crystal CuO film structure indicate the presence of not only Cu²⁺ but also Cu¹⁺ ions in the layer of CuO in close contact with Cu. Possible reasons for the appearance of paramagnetism in these systems are discussed. It is proposed that a paramagnetic layer at the contact between the antiferromagnetic copper monoxide and the other copper-oxide phases or with copper could be the cause of the impurity metastability observed previously in the high-T _c superconducting phase. Fiz. Tverd. Tela (St. Petersburg) 40, 295–298 (February 1998)