Photoluminescence of zinc oxide modified by nanopowders

The modifying effect of Al₂O₃, Al₂O₃ · CeO₂, ZrO₂, ZrO₂ · Y₂O₃ nanopowders on the photoluminescence spectra of ZnO powder in the 360–660 nm range is investigated. It is found that the introduction of nanoparticles causes a decrease in the ultraviolet band intensity and an increase in the visual spectral band intensity. The change in the intensity of elementary components of the visible range band during modification seems to be explained by the emergence of oxygen and zinc vacancies (V _O⁺ and V _Zn⁻) and interstitial oxygen ions (O _i ⁻).     

Electrical and optical spectroscopy on ZnO:Co thin films

Magnetic oxide semiconductors, for example the highly transparent and intrinsically n-type conducting zinc oxide doped with the 3d transition metal Co (ZnO:Co), are promising for the emerging field of spintronics [1]. We investigated n-conducting ZnO:Co thin films with a Co content of nominal 0.02, 0.20, or 2.00 at. %. The substitution of Co cations in the tetrahedral sites of wurtzite ZnO with Zn was confirmed at low temperature by the 1.877 eV photoluminescence between crystal field split d-levels of Co²⁺ (d⁷) ions. Based on theoretical studies, it is predicted that the formation of electron levels with zinc interstitials (I_Zn) or hole levels with zinc vacancies (V_Zn) is necessary to induce ferromagnetism, whereas the formation of electron levels with oxygen vacancies (V_O) is detrimental for ferromagnetism in ZnO:Co [2]. Cobalt generates a hole level in ZnO [3]. We investigated the generation of electron levels in n-conducting ZnO:Co in dependence on the Co content by means of deep level transient spectroscopy (DLTS). However, because of the ambiguous categorization of deep defects in n-conducting ZnO (V_O, I_Zn), an optimization of defect-related ferromagnetism in ZnO:Co is not possible at the moment. PACS 78.30.Fs; 91.60.Ed; 91.60.Mk     

Properties of the oxygen vacancy in ZnO

As-grown ZnO bulk crystals and crystals annealed in vacuum, oxygen, or zinc vapour were characterized by electrical, optical and magnetic resonance spectroscopy. The experiments show that the residual carrier concentration is caused by residual H, Al, Ga and oxygen vacancies (V_O) in the material. Annealing the samples in O₂ at about 1000 °C (2 atm, 20 h) reduces the H and V_O donor concentration by typically one order of magnitude. The photoluminescence and deep level transient spectroscopy (DLTS) results suggest a correlation between the broad unstructured emission at 2.45 eV (“green band”) and a donor level 530 meV below the conduction band, it is attributed to the V_O ^0/++transition. By using DLTS experiments with optical excitation it is possible to observe a metastable level 140 meV below the conduction band which is assigned to the V_O ^2+/+ recharging. The results give evidence for the “negative-U” properties of the oxygen vacancy defects predicted by recent theoretical calculations. PACS 71.55.Gs; 72.20.Jv; 76.30.Mi; 76.70.Hb; 78.55.Et     

Can electron paramagnetic resonance measurements predict the electrical sensitivity of SnO<Subscript>2</Subscript>-based film?

Paramagnetic singly ionized oxygen vacancies V_o and chemisorbed Sn⁴⁺-O₂⁻ species were detected by electron paramagnetic resonance measurements on SnO₂ and transition metal (Pt, Ru)-doped SnO₂ thin film that had been reduced with CO at different temperatures and then brought into contact with oxygen. The amounts of the two paramagnetic species were evaluated and are discussed as a function of the film annealing temperature in air, the reduction temperature under CO, and the type and concentration of the doping transition element. Also the structural properties of the film were identified through glancing incidence X-ray diffraction analysis. Measurements of the electrical sensitivityS(S=R _air/R _CO, whereR _air andR _CO are the resistance under air and under CO(800 ppm)/air respectively) show that the trend of the sensitivity values vs. the reduction temperature with CO could be predicted by the parallel trend of the number of Sn⁴⁺−O₂⁻ centers.     

A study of lattice defects in alkali fluorides by thermoluminescence experiments

Summary Lattice defects in KF, NaF and LiF are investigated by recording the thermoluminescent emission of X-irradiated samplesvs. temperature and wavelength. Experimental results show the presence of cation vacancies and interstitials in KF and NaF and of F⁽⁻⁾ vacancies and interstitials in NaF and LiF. In NaF, the ionization energy of V_F centres is found to be 6.4 eV, that of H centres 5.6 eV.     

μ− SR studies of oxide-superconductorsSR studies of oxide-superconductors

The negative muon spin rotation method (μ⁻ SR) has been applied to studies of electronic states at oxygen sites of oxide superconductors YBa₂Cu₃O₇, Nd_2−x Ce _x CuO_4−δ (x=0.15, oxygen reduced), LiTi₂O₄ and related oxide-insulators La₂CuO_4−δ, CuO, Cu₂O. The paramagnetic shifts of μ⁻ trapped at oxygen nuclei in these polycrystalline powder samples have been measured at 300 K. All the measured shifts are positive. In copper-oxides the paramagnetic shifts are of the order 10⁻³, while in LiTi₂O₄ is very small (8.4±3.34×10⁻⁵). In YBa₂Cu₃O₇, a fast μ⁻ spin relaxation timeT ₂ ^* (∼ 200 ns) has been observed; the reason for this is unknown and further studies are now in progress.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Room temperature photoluminescence from Zr-doped sol-gel silica

Intense room-temperature photoluminescence (PL) from the UV to the green region was observed from Zr⁴⁺-doped silica synthesized by a sol-gel process using tetraethoxysilane as the precursor, followed by thermal treatment at 500 °C in air. The wide PL band can be resolved into three components centered at 3.70, 3.25, and 2.65 eV, respectively. The intensity of the 3.25 and 2.65 eV PL bands was greatly enhanced compared with pure sol-gel silica. The 3.70 eV emission was assigned to non-bridging oxygen hole centers, while the 2.65 eV one originated from neutral oxygen vacancies (V_O). The 3.25 eV PL band was most likely associated with E′ centers, as supported by electron spin resonance measurement. It was proposed that the Zr⁴⁺-doping leads to oxygen deficiency in the silica, thus resulting in enhancement of the density of V_O and E′ center defects.     

Preparation and electrochemical properties of nano Al<Subscript>0.2</Subscript>V<Subscript>2</Subscript>O<Subscript>5.3−<Emphasis Type="BoldItalic">δ</Emphasis></Subscript> cathode materials for rechargeable lithium batteries

Nano-sized Al³⁺-doped V₂O₅ cathode materials, Al_0.2V₂O_5.3−δ , were prepared by an oxalic acid assisted sol–gel method at 350 °C (sample A) and 400 °C (sample B). X-ray diffraction confirmed that samples A and B were pure phase Al_0.2V₂O_5.3−δ with an orthorhombic structure close to that of V₂O₅. Scanning electron microscopy showed that sample A was in nanoscale with a mean particle size about 50 nm. Cyclic voltammetry showed the good electrochemical and structural reversibility of the Al_0.2V₂O_5.3−δ nanoparticles during the Li⁺ insertion/extraction process. The Al_0.2V₂O_5.3−δ nanoparticles exhibited excellent charge–discharge cycling performance and rate capability compared to that of bulky V₂O₅ electrodes. For instance, the materials delivered a reversible specific capacity about 180 mAh g⁻¹ (sample A) and 150 mAh g⁻¹ (sample B), in the potential window of 4.0–2.0 V at the current density of 150 mA g⁻¹. The Al_0.2V₂O_5.3−δ nanoparticles in particular showed almost no capacity fading for at least 50 cycles.     

Room-temperature deposition of transparent conductive Al-doped ZnO thin films using low energy ion bombardment

Al-doped zinc oxide (AZO) films are prepared on quartz substrates by dual-ion-beam sputtering deposition at room temperature (∼25°C). An assisting argon ion beam (ion energy E _i =0–300 eV) directly bombards the substrate surface to modify the properties of AZO films. The effects of assisted-ion beam energy on the characteristics of AZO films were investigated in terms of X-ray diffraction, atomic force microscopy, Raman spectra, Hall measurement and optical transmittance. With increasing assisting-ion beam bombardment, AZO films have a strong improved crystalline quality and increased radiation damage such as oxygen vacancies and zinc interstitials. The lowest resistivity of 4.9×10⁻³Ω cm and highest transmittance of above 85% in the visible region were obtained under the assisting-ion beam energy 200 eV. It was found that the bandgap of AZO films increased from 3.37 to 3.59 eV when the assisting-ion beam energy increased from 0 to 300 eV.     

Sauerstofflücken als Donatoren in Zinkoxid

Then-conductivity of zinc oxide single crystals is discussed in terms of the formation of oxygen ion vacancies,V ₀, instead of interstitial zinc ions, Zn _i ⁺ . The oxygen vacancies act as donors and may have one or two electrons depending on the degree of ionization. Zinc ion vacanciesV _Zn ^{- –} act as acceptors in the crystals.     

Influence of interatomic forces on the lattice dynamics of YBa2Cu3O7 (molecular dynamics method)

The method of molecular dynamics is used to study the dynamic properties of the high-temperature superconductor YBa₂Cu₃O₇. It is shown in the system La_2−x Sr_xCuO₄ that, due to the presence of strong anharmonism and a substantial difference in the interatomic forces, local “hot” regions arise around the Ba⁴⁺ charge defects in the CuO₂ and CuO planes, where the mean kinetic energy of the vibrations of the oxygen atoms reaches ∼0.5 eV. All other types of defects: oxygen and copper vacancies, substitutional atoms, and charge defects, do not lead to such effects. Fiz. Tverd. Tela (St. Petersburg) 41, 1729–1733 (October 1999)     

O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

Mass-spectrometric analysis of diffusion and solubility of helium in cerium-gadolinium ceramics with a submicrocrystalline structure

Diffusion and solubility of helium in Ce_0.8Gd_0.2O_{1.9 − δ} ceramics (δ = 0, 0.015) with a submicrocrystal structure are studied by thermodesorption of helium from preliminarily saturated (in the gas phase) crystals at temperatures of 613 and 673 K in the saturated pressure range 0–21 MPa. It is shown that, in this ceramics (δ = 0), the defect-trap diffusion mechanism operates. The main positions for dissolution are neutral anion vacancies formed as a result of thermal dissociation of impurity-vacancy complexes and saturated up to ∼1 × 10¹⁹ cm⁻³ at P = 6 MPa and T = 673 K. The dissociation energy of the complex and the energy of helium dissolution in the neutral anion vacancy are estimated at ∼2 eV and below −0.3 eV, respectively.     

Effect of photoexcitation on the electrical performance of ZnS: Mn thin-film electroluminescent structures

It is shown that the kinetics of the charge and current passing through a thin-film electroluminescent emitter, as well as the I-V characteristics of the emitter, greatly diverge under blue, red, and IR pulsed illumination with photon energies of ≈2.6, ≈1.9, and ≈1.3 eV, respectively, and a photon flux density of 4×10¹⁴–3×10¹⁵ mm⁻² s⁻¹. Results obtained indicate that, during the operation of the emitter, deep centers associated presumably with V _Zn ²⁻ zinc vacancies and V _S ⁺ and V _S ²⁺ sulfur vacancies exchange charge. These centers lie above the valence band by ≈1.1, ≤1.9, and ≤1.3 eV, respectively. Their concentrations are estimated as (3–4)×10¹⁶ cm⁻³ for V _Zn ²⁻ and V _S ⁺ and ≈1.5×10¹⁶ cm⁻³ for V _S ²⁺ . It is demonstrated that positive and negative space charges forming in the near-anode and near-cathode regions of the phosphor layer specify the electric performance of the emitters.     

Hf-sputtered indium oxide films doped with tin

Indium oxide films doped with tin (ITO-films) have been hf-sputtered from an 80 at-%In₂O₃/20 at-%SnO₂ target onto glass substrates. The sputter atmosphere contained mainly argon (10⁻²Torr) with addition of oxygen (0≦p _{O 2}≦2·10⁻²Torr). The sputtered films aren-conductors. The conductivity and density of charge carriers depend on the oxygen content of the sputter gas. They could be varied by two orders of magnitude. In air or in oxygen atmosphere the films oxidize at the surface and for a certain depth beneath the surface, thus decreasing the conductivity. The Hall mobility of the sputtered films is smaller (≈10 cm²V⁻¹ s⁻¹) than one observes at ITO films produced by CVD sparaying or other methods. The conductivity of as sputtered films approached maximum values of about 1000Ώ⁻¹cm⁻¹.     

Photoluminescence quenching in zinc oxide modified by Al2O3 and Al2O3 · CeO2 Nanopowders under proton irradiations

The photoluminescence spectra of initial ZnO powder and that modified by Al₂O₃, Al₂O₃ · CeO₂ nanopowders are investigated in the range 360–660 nm before and after 100-keV proton irradiation. It is found that the introduction of nanoparticles causes a decrease in the UV-band intensity and a change in the luminescence bands in the visual spectrum due to V _O ⁺ oxygen vacancies, O _int ^- interstitial oxygen, and V _Zn ^- zinc vacancies. Luminescence quenching in the UV and visible spectra occurs under the effect of protons. The decomposition of the spectra into elementary defects and analysis of changes in their integrated intensity during modification and irradiation of the powders are carried out.     

μ+SR study of vacancies in thermal equilibrium in ferromagnets

Muon spin precession frequencies and transverse relaxation rates have been measured on demagnetized iron, cobalt, and FeCo alloys (3 at%–50 at% Co) between room temperature and the Curie temperatureT _c. The increase of the relaxation rate in iron between 930 K and 1010 K could be quantitatively attributed to the trapping of positive muons by vacancies in thermal equilibrium, resulting in an enthalpy of monovacancy formation ofH _1V ^F =(1.7±0.1) eV. the smallest vacancy concentrations detected are = 10⁻⁸.     

DO<Subscript>3</Subscript>-type cubic structure of nonstoichiometric vanadium monoxide

An X-ray diffraction study indicates that nonstoichiometric vanadium monoxide VO _y ≡ V _x O _z (y = z/x) has a cubic structure of the DO₃ type (space group Fm $ \bar 3 $ \bar 3 m), where vanadium atoms are not only at the 4(a) sites of the metal fcc sublattice, but also at the tetrahedral 8(c) sites. This circumstance fundamentally distinguishes monoxide VO _y from strongly nonstoichiometric MX _y compounds with the B1 structure and the same space group, where atoms M and X and structural vacancies ▪ and ▭ of the metal and nonmetal sublattices, respectively, are distributed over the 4(a) and 4(b) sites. The dependence of the filling factor q of the tetrahedral interstices by vanadium atoms on the relative content y of oxygen in VO _y has been obtained. It has been shown that the composition of cubic vanadium monoxide should be represented as VO _y ≡ V _x O _z ≡ V _{x − 2q} V_2q ^(t)▪_{1 − x + 2q} O _z ▭_{1 − z} , taking into account the structure.     

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.