Defects in CaF2 caused by long-time irradiation and their response to annealing

Samples of CaF₂ irradiated for millions of years in nature were studied by several methods, including X-Ray diffraction, positron annihilation spectroscopy (PAS), photoluminescence spectroscopy (PLS) and transmission electron microscopy (TEM). It was found that the unexpectedly high density of radiation-induced defects present in the fluorite structure (documented by TEM) causes significant micro-strains. Even annealing up to 450°C cannot completely remove these micro-strains, which are stabilised by impurities. PAS and subsequent theoretical calculations revealed the behaviour of the defects during heating. The PL spectra of irradiated fluorite were also interpreted.     

Formation of defect structures in Au-polysilane interfaces probed by low energy positron beams

Formation and accumulation of defect structures at interfaces between polysilanes and vacuum-evaporated gold (Au) electrodes are discussed quantitatively by low energy positron annihilation spectroscopy. The size distribution of the defects at the interface is analyzed based on the values of ortho-positronium (o-Ps) lifetime (τ₃), and no effect of the evaporation process is observed in the polymer films. The intensity of o-Ps (I₃) indicates no considerable change before and after Au evaporation on dialkyl-substituted polysilanes, however, the values of I₃ is increased ∼20% in phenyl-substituted polysilane (PMPS) by the evaporation. The I₃ dependence on incident positron energy suggests the formation of the defects not only at an Au-PMPS interface but also in PMPS bulk phase as deep as 400 nm from the interface. Phenyl ring dissociation from the polymer backbone will play a significant role in the selective formation of the defects in PMPS. This is the first report on the direct measurement of defect structures at conjugated polymer-metal interface with non-destructive way, implying that electrode fabrication by vacuum evaporation affects the solid state structure of polymers.     

Positron beam studies of cobalt silicides

Silicide formation in Co/Si thin structures synthesized using thermal evaporation, sputter deposition and ion implantation, has been investigated using depth-resolved positron annihilation spectroscopy (PAS) together with other corroborative experimental techniques. S vs. E_p curves and S-W correlation plots have revealed important processes such as defect annealing, interdiffusion, silicide formation and recrystallization of amorphous Si. These studies have shown that there exist differences in the formation temperature of the silicide phases, the sequence of silicide phase formation and defect generation owing to the nature of the deposition methods employed.     

Effect of KOH molarity and annealing temperature on ZnO nanostructure properties

In this work, ZnO nanorods (NRs) were fabricated using a low cost chemical bath deposition (CBD) method. The effect of the potassium hydroxide concentration on the fabricated ZnO nanostructures was studied in depth. The optical, structure, and surface morphology properties of the fabricated ZnO nanostructures were investigated using Uv-vis spectroscopy, XRD, and SEM. The results indicate that the formation of hexagonally structured ZnO nanorods with different lengths and diameters was dependent on the KOH concentration. The sample prepared with 2 M of KOH was the best one for optoelectronic applications, since it has the smallest diameters. This sample was annealed at different temperatures (473 K–1073 K). Positron Annihilation Lifetime Spectroscopy was used to determine the defects in the ZnO nanorods. The results show that the positron mean lifetime (τ_m) decreased as the annealing temperature increased, which means that the overall defects in the ZnO nanorods decreased with increasing temperature. Consequently, higher performance semiconductor devices based on ZnO nanorods could be fabricated after high annealing of the ZnO nanorods.     

Cu/ZnO(0001̄) and ZnOx/Cu(111): Model catalysts for methanol synthesis

In an attempt to understand the relative importance of the various constituents of copper-zinc oxide catalysts for methanol synthesis (2H₂ + CO → H₃COH), we have prepared and characterized a number of single-crystal surface structures of Cu-ZnO. The model catalysts have also been tested in terms of their activity for methanol synthesis. The growth of vapor-deposited Cu overlayers on a ZnO(0001&#x0304;) (O face) single crystal has been investigated using X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), He⁺ ion scattering spectroscopy (ISS) and low-energy electron diffraction (LEED). The results are consistent with a growth model in which, at room temperature, the first monolayer spreads uniformly across the surface in a p(1 × 1) structure. As more Cu is added, thick Cu(111) islands grow and these are separated by large regions of the p(1 × 1)-Cu monolayer. The Cu(111) islands are rotationally aligned with the ZnO substrate, and at high enough coverages grow together to cover the ZnO. Increasing temperature favors more agglomeration. A clean Cu(111) crystal and one containing a ZnO_x (x ⋍ 3) monolayer were also studied. None of these model catalysts gave rates of methanol production which were measurable in our present experimental limits (TOF < 2 × 10⁻³ molecules site⁻¹ s⁻¹) at 500–600 K and CO + H₂ pressures up to 1500 Torr. Under these “reaction” conditions, the Cu in direct contact with ZnO may be slightly oxidized; all the other Cu is completely metallic. The Cu does not change its character between deposition and reaction conditions, even if heavily oxidized to CuO in between. The addition of CO₂ at very high levels under reaction conditions does not change the character of a Cu(111) model catalyst surface, and no surface oxygen is ever observable after treatment under reaction conditions.     

Vacancy defects in (Zn, Mn)O

We have used positron annihilation spectroscopy to study the vacancy defects in (Zn, Mn)O crystals grown by chemical vapor transport (CVT). Our results show that Zn vacancies are present in both as-grown and high temperature annealed ZnO and Zn_0.985Mn_0.015O. In addition, we observe O vacancies in ZnO with no Mn. After annealing in O₂ at 1000 C, there is no change in the vacancy distribution in ZnO, while the Zn vacancy concentration increases by an order of magnitude in Zn_0.985Mn_0.015O.     

Superhydrophobic surfaces based on dandelion-like ZnO microspheres

This study presents a simple method to fabricate superhydrophobic surface based on ZnO nanoneedles. ZnO nanoneedles had been constructed on zinc layers by immersing in an aqueous NH₄OH solution at 80 °C. The ZnO films were characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. The ZnO films exhibited excellent superhydrophilicity (contact angle for water was 0°), while they changed wettability to superhydrophobicity with a water contact angle greater than 150° after further chemical modification with n-dodecanoic acid. The procedure reported here only needs readily available reagents and laboratory equipments, which can be applied to various substrates of any size and shape.     

Defect studies of hydrogen-loaded nanocrystalline Gd films

The present work reports on microstructure investigations of hydrogen-loaded nanocrystalline Gd films by means of slow positron implantation spectroscopy combined with in situ synchrotron radiation X-ray diffraction. It is found that the virgin films contain a high density of vacancy-like open volume defects at grain boundaries which trap positrons. These defects represent trapping sites also for hydrogen. With increasing hydrogen concentration the transformation from the α- into the β-phase (GdH₂) takes place in the film. Accumulation of hydrogen at grain boundaries causes a decrease of positron localization at defects. The transformation into the β-phase is completed at x_H ≈ 1.6 H/Gd. Contrary to bulk Gd specimens, the γ-phase (GdH₃) is not formed in the nanocrystalline Gd films.     

ZnO-treated TiO2 inverse opal electrodes for dye-sensitized solar cells

We report that the photovoltaic properties of inverse opal TiO₂ (io-TiO₂) electrodes in dye-sensitized solar cells can be enhanced by ZnO treatment of the inverse opal structures. ZnO was coated on the surface of io-TiO₂ via the sol–gel reaction of ZnO precursors. Energy dispersive X-ray spectroscopy (EDX) measurements showed that the amount of ZnO on the io-TiO₂ surface was measured to be 0.12–0.50 wt% of zinc, depending on the number of coatings. Compared to bare inverse opal electrodes, the energy conversion efficiency of cells increased for the 0.35 wt% ZnO-coated electrodes, and then decreased for the 0.50 wt% ZnO-coated electrodes. The maximum efficiency of 5.3% was achieved, corresponding to a 23% increase in efficiency compared with bare io-TiO₂ electrodes. The enhanced efficiency was mainly attributed to the improvement of the open-circuit voltage (V_OC). EIS and dark current measurements confirmed that this enhancement in V_OC was due to the movement of the conduction band edge in a negative direction after ZnO treatment, rather than the formation of a barrier layer for electron recombination.     

Applications of slow positrons to cancer research: Search for selectivity of positron annihilation to skin cancer

Slow positrons and positron annihilation spectroscopy (PAS) have been applied to medical research in searching for positron annihilation selectivity to cancer cells. We report the results of positron lifetime and Doppler broadening energy spectroscopies in human skin samples with and without cancer as a function of positron incident energy (up to 8 μm depth) and found that the positronium annihilates at a significantly lower rate and forms at a lower probability in the samples having either basal cell carcinoma (BCC) or squamous cell carcinoma (SCC) than in the normal skin. The significant selectivity of positron annihilation to skin cancer may open a new research area of developing positron annihilation spectroscopy as a novel medical tool to detect cancer formation externally and non-invasively at the early stages.     

Hierarchical ZnO/Bi2O3 nanostructures: synthesis, characterization, and electron-beam modification

Two types of ZnO/Bi₂O₃ nanonecklace heterostructures were fabricated using the vapor-phase transport (VPT) method for the first time. These hierarchical structures were well characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS) attached. The growth mechanism of the novel structures were proposed based on these characterizations. Electron-beam irradiation was found to be a powerful and controllable tool in further tailoring such ZnO/Bi₂O₃ nanonecklace heterostructures. In addition, photoluminescence (PL) emission from the hierarchical nanostructures showed enhancement comparing to the pure Bi₂O₃ powder.     

Thermal stability of grain boundaries in nanocrystalline Zn studied by positron lifetime spectroscopy

Nanocrystalline Zn prepared by compacting nanoparticles with mean grain size about 55 nm at 15 MPa has been studied by positron lifetime spectroscopy. For the bulk Zn sample, the vacancy defect is annealed out at about 350 °C, but for the nanocrystalline Zn sample, the vacancy cluster in grain boundaries is quite difficult to be annealed out even at very high temperature (410 °C). In the grain boundaries of nanocrystalline Zn, the small free volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ₁). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τ_av), which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. This stabilization is very important for the nanocrystalline materials using as radiation resistant materials.     

Temperature dependence and the effect of hydrogen peroxide on ITO/poly-ZnO Schottky diodes fabricated by laser evaporation

Transparent and efficient poly-ZnO ultraviolet Schottky diodes grown at different temperatures with indium-tin-oxide (ITO) as the metallic contact layer were fabricated with hydrogen peroxide (H₂O₂) applied as a surface treatment at 70 °C for 20 min. Analysis via field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) demonstrated that the ZnO films underwent gradual oxidation and that H₂O₂ treatment resulted in an interfacial ZnO₂ layer that covered the ZnO surface. I–V measurements indicated that the ideality factor and the Schottky barrier height improved with increasing shunt resistance, and the trade-off between film quality and the degree of oxidation revealed that films grown at 400 °C exhibited the best diode characteristics.     

Top electrode-dependent resistance switching behaviors of lanthanum-doped ZnO film memory devices

Lanthanum-doped ZnO (Zn_0.99La_0.01O) polycrystalline thin films were deposited on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method. Metal/La-doped ZnO/Pt sandwich structures were constructed by depositing different top electrodes (Ag and Pt). Unipolar switching and bipolar switching characteristics were investigated in Pt/La-doped ZnO/Pt and Ag/La-doped ZnO/Pt structures, respectively. Compared with the undoped devices (Pt/ZnO/Pt and Ag/ZnO/Pt), the La-doped devices exhibits superior resistive switching performances, such as narrow distribution of the resistive switching properties (R _ON, R _OFF, V _Set, and V _Reset), higher R _OFF/R _ON ratio and sharp switching transition.     

Shuttle-like ZnO nano/microrods: Facile synthesis, optical characterization and high formaldehyde sensing properties

Shuttle-like ZnO nano/microrods were successfully synthesized via a low temperature (80 °C), “green” (without any organic solvent or surfactant) and simple hydrothermal process in the solution of zinc chloride and ammonia water. X-ray diffraction and Raman spectroscopy indicated that the ZnO nano/microrods are a well-crystallized hexagonal wurtzite structure. Yet photoluminescence analysis showed that abundant intrinsic defects (52.97% electron donor defects and 45.49% electron acceptor defects) exist on the surface of ZnO crystals. Gas sensors based on the shuttle-like ZnO nano/microrods exhibited high sensitivity, rapid response-recovery and good selectivity to formaldehyde in the range of 10-1000 ppm at an optimum operating temperature of 400 °C. Through applying linear fitting to the plot of sensitivity versus formaldehyde concentration in logarithmic forms, the chemisorbed oxygen species on the ZnO surface were found to be O²⁻ (highly active among O₂, O₂⁻ and O⁻ species). Notably, formaldehyde can be easily distinguished from acetaldehyde with a selectivity of about 3. The high formaldehyde sensitivity is mainly attributed to the synergistic effect of abundant electron donor defects (52.97%) and highly active oxidants (surface adsorbed O²⁻ species) co-existed on the surfaces of ZnO.     

Positron study of radiation embrittlement of steels used in water cooled, water moderated energy reactors

Positron annihilation spectroscopy (PAS) lifetime study was applied in the evaluation of the microstructure parameters and degradation processes of nuclear reactor pressure vessel (RPV) steel surveillance specimens. Study was oriented to the material investigation of Russian WWER-1000 steels (15Kh2MNFAA and 12Kh2N2MAA) with higher Ni content (1.26 wt.% in base metal and 1.7 wt.% in weld). For comparison, the WWER-440 weld metal (Sv10KhMFT) without Ni was measured too. Specimens were studied in as received stage, after irradiation in LVR-15 experimental reactor to the neutron fluence F_{(E > 0.5 MeV)} = 4 × 10²³ m⁻² s⁻¹ and after annealing in vacuum at 475 °C/2 h. Post-irradiation thermal treatment and annealing of defects was well detected by different PAS techniques. It was observed that the sensitivity of PAS parameters to defined irradiation treatment decreases with Ni-content increase. Results confirm the hypothesis that Ni affects size (decrease) and distribution (more homogeneous) of the Cu- and P-rich clusters and M_xC_x carbides.     

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L_3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2p-derived states through O 2p-Cr 3d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr₂O₃ phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr₂O₃, whereas the bulk comprise phase segregations of Cr₂O₃ and/or ZnCr₂O₄, which results them the most stable TM-doped ZnO material against etching.     

Memristive Effect in Two-Layered Structures Based on Lithium Doped ZnO Films

The structure of Au/Li10ZnO/Li1ZnO/LaB₆ consisting of upper Au and lower LaB₆ ohmic electrodes and a p-n junction p-Li10ZnO/n-Li1ZnO, which has the resistive memory where two functions are simultaneously combined, that is, an address access and the process of reading and storing of information is investigated. The resistance ratio (R_reset/R_set = 10), the data storage time (> 3 hours) and the number of switching cycles (> 350) are improved as compared to the corresponding single-layer structures. The resistive memory is explained by the modulation effect of the Li10ZnO layer, the ferroelectric polarization of which, depending on the orientation, changes the width and height of the barrier of the p-n junction formed at the p-Li10ZnO/n-Li1ZnO contact.     

正电子湮没谱和光致发光谱研究掺锌GaSb质子辐照缺陷

用正电子湮没谱和光致发光谱研究了质子辐照后掺锌GaSb中的缺陷.通过分析正电子的缺陷寿命τ₂及强度I₂的变化发现,在高能质子的辐照下产生了双空位缺陷V_GaV_Sb,可能同时产生了小的空位团.正电子平均寿命τ_av和S参数随着质子辐照剂量的变化也证明了这一结论.通过分析不同质子辐照剂量下掺锌GaS     

Tailoring Cu2−xTe quantum-dot-decorated ZnO nanoparticles for potential solar cell applications

Cu_2−xTe QDs on ZnO nanoparticles were synthesized using a successive ionic layer absorption and reaction technique (SILAR) at room temperature. The as-synthesized QDs which were distributively deposited on ZnO nanoparticles surface were characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction and high-resolution transmittance microscope (HR-TEM). It revealed that the average diameter of the QDs was ∼2 nm. The synthesized Cu_2−xTe QDs were solely orthorhombic Cu_1.44Te phase. The growth mechanism was supposed that it based on ions deposition. The energy gap of as-synthesized Cu_2−xTe QDs was determined ∼1.1 eV and the smallest energy gap of 0.76 eV was obtained, equal to that of bulk material. Raman spectroscopy and FTIR were also used to study the Cu_2−xTe QDs on ZnO nanoparticles. These characteristics suggest a promising implication for a potential broadband sensitizer of QDSCs.