Phase transformations in CuO caused by bombardment by He<Superscript>+</Superscript> ions and by the action of spherical shock waves

The valence state of copper ions and the phase composition of copper monoxide CuO subjected to bombardment by He⁺ ions and explosive shock waves are studied by the methods of x-ray photoelectron spectroscopy (XPS) and x-ray emission spectroscopy (XES). Measurements of photoelectron Cu 2p and emission O K_α spectra revealed a decrease in the concentration of Cu²⁺ ions and partial reduction of CuO to Cu₂O as a result of both ion bombardment and shock-wave loading. The concentration of the Cu₂O phase attained values of 10–15%. The Cu₂O phase is revealed by the XPS and XES methods even at concentrations lower than its threshold concentration for detection by x-ray diffraction measurements. This points to the effectiveness of XPS and XES techniques in studying nanocrystalline materials and defect structures containing finely dispersed inclusions. A model for the emergence of Cu₂O due to the formation of charged clusters under the action of stress waves is proposed.     

Magnetic properties of xCuO · (1 - x) [2B2O3 · PbO] glasses

The results of magnetic studies on xCuO · (1 ? x) [2B₂O₃ · PbO] glasses with 0 ? x ? 50 mol.%, are reported. These results evidenced that the copper ions, in this glass system, are in Cu²⁺ and Cu⁺ valence states. From Curie constant is determined the amount of the copper ions in bivalent state. For glasses with x > 5 mol.% CuO, an antiferromagnetic behaviour is evidenced.     

Spectroscopical splitting of Cu ion energy levels in magnesium lead fluoro silicate glasses

Homogeneous 40.0 MgO-(10-x) PbF₂-50.0 SiO₂: x CuO glasses were prepared using melt-quenching technique under controlled conditions. Spectroscopic studies (UV-vis absorption, ESR, FT-IR) are carried out for these glasses. One broad characteristic visible absorption band is observed around 700-850 nm in these glasses, the optical band gap decreases as the content of the CuO increases in the glass network up to 0.7 mol % then reversal trend is observed. ESR spectra of all these glasses show resonance peaks characteristic of Cu²⁺ ions and hyperfine splitting is resolved with increasing the CuO content in the glass network. From the observed ESR spectra, the spin-Hamiltonian parameters have been evaluated and indicate that Cu²⁺ ions have octahedral coordination with a strong tetragonal distortion in these glasses. By correlating ESR and optical absorption data, the molecular orbital coefficients have been evaluated. FT-IR spectra give important information about the nature of bonds in the glass matrix. The density of the glasses is also measured and is found to decrease with the increase CuO contents in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

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).     

Effect of CuO addition on the optical and electrical properties of sodium zinc borophosphate glasses

Sodium borophosphate glasses doped with copper ions having general composition 20Na₂O-20ZnO-25B₂O₃-(35-x) P₂O₅-x CuO (x=1-8 mol %) were prepared using conventional melt-quench method and characterized by density, UV-visible optical absorption, photoluminescence and conductivity measurements. E_optical values for different glass samples are found to decrease systematically from 3.5 to 2.5 eV with increase in CuO content in the glass. Network modifying action of CuO with the glass network has been confirmed from the UV-visible optical absorption studies. Presence of Copper in the form of Cu⁺ species has been confirmed from photoluminescence measurements. The electrical conductivity (σ) increases with increase in copper oxide content in the glass and temperature dependence of electrical conductivity confirmed the semiconducting nature of the samples.     

Potential dependence of cuprous/cupric duplex film growth on copper electrode in alkaline media

The duplex oxide film potentiostatically formed on copper in concentrated alkaline media has been investigated by XRD, XPS, negative-going voltammetry and cathodic chronopotentiometry. The interfacial capacity was also measured using fast triangular voltage method under quasi-stationary condition. The obvious differences in the thickness, composition, passivation degree and capacitance behavior were observed between the duplex film formed in lower potential region (−0.13 to 0.18 V versus Hg|HgO electrode with the same solution as the electrolyte) and that formed in higher potential region (0.18-0.60 V). Cuprous oxides could be formed and exist stably in the inner layer in the both potential regions, and three cupric species, soluble ions and Cu(OH)₂ and CuO, could be independently produced from the direct oxidation of metal copper, as indicated by three pairs of redox voltammetric peaks. One of the oxidation peaks appeared only after the scan was reversed from high potential and could be attributed to CuO formation upon the pre-accumulation of O²⁻ ions within the film under high anodic potentials. A new mechanism for the film growth on the investigated time scale from 1 to 30 min is proposed, that is, the growth of the duplex film in the lower potential region takes place at the film|solution interface to form a thick Cu(OH)₂ outer layer by field-assisted transfer of Cu²⁺ ions through the film to solution, whereas the film in the higher potential region grows depressingly and slowly at the metal|film interface to form Cu₂O and less CuO by the transfer of O²⁻ ions through the film to electrode.     

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.     

Fabrication of cuprous and cupric oxide thin films by heat treatment

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were prepared by thermal oxidation of copper films coated on indium tin oxide (ITO) glass and non-alkaline glass substrates. The formation of Cu₂O and CuO was controlled by varying oxidation conditions such as, oxygen partial pressure, heat treatment temperature, and oxidation time. The microstructure, crystal direction, and optical properties of copper oxide films were measured with X-ray diffraction, atomic force microscopy, and optical spectroscopy. The results indicated that the phase-pure Cu₂O and CuO films were produced in the oxidation process. Optical transmittance and reflectance spectra of Cu₂O and CuO clearly exhibited distinct characteristics related to their phases. The electrical properties indicated that these films formed ohmic contacts with Cu and ITO electrode materials. Multilayers of Cu₂O/CuO were fabricated by choosing the oxidation sequence. The experimental results in this paper suggest that the thermal oxidation method can be employed to fabricate device quality Cu₂O and CuO films that are up to 200–300 nm thick.     

The hole concentration on oxygen sites in the highT c superconductor Y1−Ba2−Cu3−O7−x

From XPS core level spectroscopy the average copper charge on the Cu sites in the high temperature superconductor Y₁Ba₂Cu₃O_7–x is determined as function of the oxygen vacancy concentrationx. Analysis of these data leads to the suggestion that there are holes on the oxygen sites in the basal plane of the crystal structure. The probability for holes on these oxygen ions is rather constant for 0x0.3 with a value of 0.64 and decreases to zero forx=0.5. The dependence of the superconducting transition temperature on the hole concentration is discussed. An energy level diagram for Cu²⁺ and Cu³⁺ in YBa₂Cu₃O_7–x is constructed.     

Development of the method for low-temperature investigations of HTSC systems on an X-ray electron magnetic spectrometer

Peculiarities of the chemical structure of bulk polycrystalline samples of the high-temperature superconductors Bi₂Sr₂CaCu₂O₈, BiSrCaCu₂O_5.5, BiSrCaCu₃O₈, and YBa₂Cu₃O_{7 ? δ} have been investigated in detail at room and superconducting temperatures on an X-ray electron magnetic spectrometer equipped with an attachment for low-temperature studies. It is shown that covalent bonding is formed at a superconducting temperature between copper and oxygen due to Cu²⁺ ions. Due to the enhancement of the d(Cu)–p(O) hybridization of copper and oxygen electrons in the superconducting state, the d-electron density increases near E _F. The occurrence of additional peaks in the O1s and Sr3d (Ba3d) spectra after transition of the system to the superconducting state indicates changes in the nearest environment of O and Sr (Ba) atoms, in particular, the transition of Sr atoms to a higher oxidation state.     

EPR and magnetic susceptibility studies of xCuO·(1−x)[2B2O3·Li2O] glasses

The results of EPR and magnetic susceptibility studies on xCuO·(1?x)? [2B₂O₃·Li₂O] glasses with $\text{0?x?30 mol \%}$, are reported. The modification of EPR spectra with the increasing of CuO content are explained supposing that these are the result of the superposition of two EPR signals, one showing the hyperfine structure typical for isolated Cu²⁺ ions and other consisting from a broad line centered at g ～ 2 typical for the clustered Cu²⁺ ions. The values of the EPR parameters prove that the coordination of isolated Cu²⁺ -complexes remains approximately the same and show that Cu²⁺ ions are situated in axially distorted octahedral vicinities. EPR measurements have shown that the Cu²⁺ ions are present mostly as the isolated species when $\text{x?5 mol \%}$. Beside the dipole-dipole coupling between Cu²⁺ ions, the magnetic measurements suggest that for x>10 mol % superexchange interactions appear, too. From Curie constant is established that in this glass system the copper ions are in Cu²⁺ and Cu⁺ valence states. Also, the amounts of the copper ions in bivalent state are determined.     

Optical and other spectroscopic studies of lead, zinc bismuth borate glasses doped with CuO

10MO·20Bi₂O₃·(70−x)B₂O₃·xCuO [M=Pb, Zn] with x=0, 0.4 and 0.8 (wt%) glasses were synthesized by the melt-quenching technique and were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Physical parameters, like density, and spectroscopic studies (optical absorption, EPR, FTIR and photoluminescence) were used to understand the role of modifier oxide and CuO in the glass matrix. A red shift of the absorption band corresponds to ²B_1g→²B_2g transition of Cu²⁺ ions from P2 to Z4 samples and the increase of hyperfine splitting factor (A_‖) from P2 to Z2 shows that with the integration of PbO by ZnO the electron density around copper ion is increased. It is also supported by the gradual increase in theoretical optical basicity values of ZnO mixed glasses, as compared to that of PbO mixed glass matrix. Reduced bismuth radicals are found in undoped and 0.4% CuO doped glasses of both the series. Analysis of the absorption and emission studies indicates that the concentration of luminescence centers of bismuth ions (Bi³⁺ ions in UV region) is decreased by the integration of ZnO as well as by increasing the dopant concentration. In lead series PbO₄ and BiO₃ units are increased from P2 to P4 and in zinc series BiO₃ units are decreased from Z0 to Z4. The conductivity of the glass matrices is increased in both the series with the dopant of CuO.     

The effect of CuO and MgO impurities on the optical properties of lithium potassium borate glass

Previous study proved the efficiency of copper as one of the most luminescent activators. In this work, Li₂CO₃–K₂CO₃–H₃BO₃ (LKB) glasses co-doped with copper oxide (CuO) and magnesium oxide (MgO) have been prepared by chemical quenching technique. Two techniques have been applied to investigate the effect of co-dopants on the physical and optical properties of the new glass network. The X-ray Diffraction (XRD) results showed the amorphous nature of the sample. Fourier transform infrared (FTIR) spectra, energy band gap, density, ion concentration, molar volume, Polaron radius and inter-nuclear distance have been analyzed in the light of the different oxidation states of co-doped ions in the glass matrix. The exchange in the concentration of magnesium and copper ions illustrated the great effect of magnesium as a co-dopant on the Photoluminescence (PL) emission of LKB doped with copper oxide. Due to the change in the copper concentration, a broad green emission with intensity of around 300 (a.u) has been observed. Enhancement of about three times has been shown with the increment of 0.1 mol% of CuO and MgO as a co-dopant technique. It is well known that magnesium oxide alone does not show strong-luminescence, but during this increment, MgO acted as activator (co-dopant) for Cu ions. This enhancement may contribute to the energy transfer from Mg²⁺ ions to monovalent Cu⁺ ion. The current results are discussed and compared with other related studies.     

A photoemission study (XPS and UPS) of the superconductor ErBa2Cu4O8 and comparison with YBa2Cu3O7-δ(δ≈0,1)

Core level and valence band photoemission spectra of the 124 superconductor ErBa₂Cu₄O₈ are investigated using MgK , HeI, and HeII radiation and compared with photoemission spectra of orthorhombic YBa₂Cu₃O₇ and tetragonal YBa₂Cu₃O_6.2 samples. It is found that the Cu 2p _3/2 core level and the UPS valence band spectra of ErBa₂Cu₄O₈ and YBa₂Cu₃O₇ are very similar but differ significantly from those of YBa₂Cu₃O_6.2. From the resemblance between the ErBa₂Cu₄O₈ and YBa₂Cu₃O₇ spectra it follows that the electronic structures of these two compounds are closely related in spite of an additional CuO chain in the 124 phase. The differences between the YBa₂Cu₃O_6.2 spectra and the other spectra are explained by the the presence of monovalent copper at the crystallographic Cu(1) sites. The Cu 2p _3/2 lineshapes of the here studied superconductors and some Cu^II compounds are discussed.     

On theg≃2 ESR resonance in YBa2Cu3O7-y high-T c superconductor

Various samples of single-phase YBa₂Cu₃O_7–y have been examined by X-band ESR in theg2 region forTT _c .The observed spectra are attributed to oxygen coordinated Cu²⁺ ions with a large delocalization of the unpaired spins. These are probably due, in part, to the inclusion of some impurity phase. However, an analysis of the intensity as a function of the temperature in different samples indicates that a possible intrinsic contribution to the ESR signal of Cu²⁺ ions from the superconducting phase is due, at most, to 1% of the total copper in the formula. This small quantity of isolated Cu²⁺ ions may be due to the presence of low symmetry Cu³⁺ ions or, equivalently, non-magnetic centers such as Cu²⁺–O^– pairs in the chains.CISM (M.P.I.) and GNSM (C.N.R.)     

X-ray photoelectron spectroscopy of the high-temperature superconductor YBa2Cu3O7−x and the copper oxides

The X-ray photoelectron (XPS) core-level spectra of Cu-metal, Cu₂O, CuO, NaCuO₂ and YBa₂Cu₃O_7–x have been determined. It has been shown, that the Cu³⁺ ions in NaCuO₂ are reduced to lower valence states by X-rays in ultrahigh vacuum (UHV). The determination of the electron binding energy of the Cu 2 _{p 3/2} level in NaCuO₂ yields a value of 934.1 eV. The shape of the Cu 2 _{p 3/2} peak as well as the appearence of a shake-up satellite in YBa₂Cu₃O_7–x which is smaller than in CuO show that YBa₂Cu₃O_7–x contains Cu³⁺ ions. The behaviour of YBa₂Cu₃O_7–x also was studied during X-ray irradiation and a reduction was noticeable.     

Lack of delocalized Cup states at the fermi level in the high-T c superconductor YBa2Cu3O∼7 by XANES spectroscopy

The x-ray absorption spectra of the single phase high temperature superconducting YBa₂Cu₃O₇ withT _{c, onset}=97 K have been measured between 30 K and 300 K by using synchrotron radiation.The copperK-edge x-ray absorption near edge structure (XANES) spectrum gives experimental evidence of the lack of delocalized Cup states close to the Fermi level, in fact a spectral distribution of local (at the Cu site) partial (l=1) density of states as in the insulating CuO has been found.The EXAFS (extended x-ray absorption fine structure) spectrum shows evidence of the formation of layers formed by Cu ions coordinated by oxygen square planes sharing corners. The average Cu–O distance at 30 K in the layers has been found to be 1.93 i.e. 0.02 shorter than in CuO and the average distance between Cu ions at the centers of the square planes is 3.85.The present local structure suggests that superconductivity should occur in the crystalline planes formed by CuO₄ square plane units. The lack of delocalized Cu states is in agreement with the hypothesis that conductivity is due to itinerant holesL in the oxygen derived valence band.The results of this experiment have been presented at the Symposium on the Latest Developments in Superconductivity at High Temperatures of the European Physical Society Meeting held in Pisa april 8, 1987     

Classical trajectory calculations of the energy distribution of ejected atoms from ion bombarded single crystals

The energy distribution of particles ejected from single crystal surfaces has been calculated using classical dynamics. The model utilizes a microcrystallite of 4 layers with ~60 atoms/layer which is bombarded by 600 eV Ar⁺ at normal incidence. Calculations have been performed for the clean (100) face of copper as well as for copper with oxygen placed in various coverages and site geometries. The energy distributions for Cu, O, Cu₂, CuO and Cu₃ are reported for this system. The distribution for clean Cu exhibits structure which is shown to arise from preferred ejection mechanisms in the crystal. For oxygen adsorbates, the effect of the oxygen binding energy on the peak in the energy distribution of the ejected oxygen atoms is examined by arbitrarily varying the well-depth of the Cu-O pair potential. In general, higher values of the binding energy produce a maximum in the curve at higher energies and also produce a broader energy distribution. The O₂ and Cu₂ dimer distributions are found to peak at approximately the same energy as the O and Cu curves when compared on a kinetic energy/particle basis, although their widths are considerably smaller. Finally, we predict that the CuO energy distribution should be wider than either the Cu₂ or O₂ distributions since it results from the convolution of the Cu and O distributions which are quite different.     

Formation and its mechanism of copper metal layers at surface by annealing in reduced atmosphere in CuO–Li2O–Nb2O5–SiO2 glass

A trace amount (0.5 mol%) of CuO-doped 40Li₂O–32Nb₂O₅–28SiO₂ glass (mol%) exhibits the formation of copper metal layers at the glass surface by annealing at temperatures (530 °C) below the glass transition temperature (544 °C) in the reduced atmosphere of 7% H₂–93%Ar. The coordination state of copper ions is examined from optical absorption and Fourier transform infrared (FT-IR) spectrum measurements, indicating the formation of Si–OH and Si–H bonds due to the diffusion of hydrogen into the inside of the glass and the reduction of Cu⁺ and Cu²⁺ ions. The mechanism of the formation of copper metals at the surface is proposed, in which the key points are the reduction of Cu²⁺ to Cu⁺ ions due to the hydrogen and the migration of Cu⁺ ions in the interior of the glass to the surface. The first finding on copper metal layers at the glass surface might have a potential for practical applications such as electrodes in glass.     

Growth, EPR and optical absorption spectra of l-threonine single crystals doped with Cu ions

We investigated the crystal growth, electron paramagnetic resonance (EPR) and optical absorption spectra of l-threonine doped with Cu²⁺. The quality, size and habit of the single crystals grown from aqueous solution by the slow solvent evaporation and by the cooling methods vary when the impurities are introduced during the growth process. The variations with the magnetic field orientation of the EPR spectra of single-crystal samples at room temperature and 9.77 GHz in three crystal planes (ab, bc and ac) show the presence of copper impurities in four symmetry-related sites of the unit cell. These spectra display well resolved hyperfine couplings of the of Cu²⁺ with the I_Cu= of the copper nuclei. Additional hyperfine splittings, well-resolved only for specific orientations of the magnetic field, indicate that the copper impurity ions in the interstitial sites have two N ligands with similar hyperfine couplings. The principal values of the g and A_Cu tensors calculated from the EPR data are g₁=2.051(1), g₂=2.062(2), g₃=2.260(2), A_Cu,1=16.9(5)×10⁻⁴ cm⁻¹, A_Cu,2=21.8(6)×10⁻⁴ cm⁻¹, A_Cu,3=180.0(5)×10⁻⁴ cm⁻¹. The principal directions corresponding to g₃ and to A_Cu,3 are coincident within the experimental errors, reflecting the orientation of the bonding planes of the copper ions in the crystal. The values of the crystal field energies are evaluated from the optical absorption spectrum, and the crystal field and bonding parameters of the Cu impurities in the crystal are calculated and analyzed. The EPR and optical absorption results are discussed in terms of the crystal structure of l-threonine and the electronic structure of the Cu²⁺ ions, and compared with data reported for other systems. The effects of the impurities in the growth and habit of the crystals are also discussed.