Evaluating the electric property of different crystal faces and enhancing the Raman scattering of Cu2O microcrystal by depositing Ag on the surface

The surface electric property of Cu₂O microcrystal affects the interaction of facets with substance in the aqueous solution, and hence plays a key role in determining the photocatalytic activity. In this paper, the capability of Cu₂O microcrystals with exclusive {111}, {110} or both lattice surfaces in reducing Ag⁺ to Ag⁰ were investigated. Ag particles selectively deposited on {111} surfaces of Cu₂O, while not on {110} surfaces. The different behaviors of the two surfaces are mainly attributed to their different electric properties: negatively-charged {111} surfaces absorb Ag⁺ ions while positively-charged {110} surfaces repel them. Raman scattering of Cu₂O {111} surfaces was enhanced by the photo-deposition of Ag particles.     

反应气压对直流磁控反应溅射制备的氧化银薄膜的结构和光学性质的影响

利用直流磁控反应溅射技术,通过调节反应气压(RP),在250 ℃衬底温度下制备了一系列氧化银 (Ag_xO) 薄膜,并利用X射线衍射谱、能量色散谱和分光光度计重点研究了RP对Ag_xO薄膜的结构和光学性质的影响. 研究结果表明,随着RP从0.5 Pa升高到3.5 Pa,薄膜明显呈现了从两相(AgO+Ag₂O)到单相(Ag₂O)结构再到两相(Ag₂O+AgO)结构的演变. 特 关键词： 氧化银薄膜 直流磁控反应溅射 X射线衍射谱 光学性质     

Influence of Ag2O on crystallisation and structural modifications of phosphate glasses

A series of phosphate glasses of composition 45P₂O₅–(40???x)CaO–15Na₂O–xAg₂O (x?=?0, 3, 6, 8, 10 and 12?mol%) with different Ag₂O contents were prepared using the melt-quenching technique. The incorporated Ag₂O highly influenced the increase of its transition tendency towards crystallisation and, on contrary, reduced the degree of glassification of phosphate glasses. The lowering of glass transition temperature and increase in thermal expansion were observed in glasses against Ag₂O inclusions. The crystalline phase transitions of amorphous material during thermal treatment were confirmed by employing X-ray diffraction studies. As revealed by X-ray photoelectron spectroscopy, the incorporated silver oxide into phosphate glass exists in two different oxidation states, Ag₂O and AgO. The pyrophosphate and metaphosphate units were predominantly occupied in glass and glass ceramics. The elastic moduli and Vicker's hardness values exhibited the decrease in phosphate glass structural compactness due to Ag₂O-incorporation and these values were found to improve because of crystalline transitions.     

Effects of the sputtering power on the crystalline structure and optical properties of the silver oxide films deposited using direct-current reactive magnetron sputtering

This paper reports that a series of silver oxide (Ag_xO) films are deposited on glass substrates by direct-current reactive magnetron sputtering at a substrate temperature of 250 oC and an oxygen flux ratio of 15:18 by modifying the sputtering power (SP). The Ag_xO films deposited apparently show a structural evolution from cubic biphased (AgO + Ag₂O) to cubic single-phased (Ag₂O), and to biphased (Ag₂O + AgO) structure. Notably, the cubic single-phased Ag₂O film is deposited at the SP = 105 W and an AgO phase with <220> orientation discerned in the Ag_xO films deposited using the SP > 105 W. The transmissivity and reflectivity of the Ag_xO films in transparent region decrease with the increase the SP, whereas the absorptivity inversely increases with the increase of the SP. These results may be due to the structural evolution and the increasing film thickness. A redshift of the films' absorption edges determined in terms of Tauc formula clearly occurs from 3.1 eV to 2.73 eV with the increase of the SP.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.     

Low-Temperature Oxidation of Polycrystalline Silver in Water Vapor

X-ray photoelectron spectroscopy and electron Auger spectroscopy are used to study the surface layers of polycrystalline silver after exposure to water vapor. It is shown that molecular oxygen, atomic oxygen in the composition of AgO and Ag₂O, and silver in the zero-valence state are present in the surface region, and also the presence of associated oxygen forms in Ag⁰–O _x -peroxide, superoxide, and ozonide structures is possible.     

Electric field gradients of 111Cd in the copper oxides CuO and Cu2O

Perturbed angular correlation measurements were performed after ¹¹¹In implantation into CuO and Cu₂O powder samples and 1 μm thick Cu₂O surface layers. The quadrupole hyperfine interaction of ¹¹¹Cd was studied in isochronal annealing cycles at 370–1170 K covering the CuO→Cu₂O phase transition. The electric field gradients obtained for ¹¹¹Cd on substitutional Cu lattice sites were associated with the repective oxygen coordinations. Annealing of Cu₂O surface layers on copper foils resulted in a texture with the efg pointing preferentially out of the surface plane.     

Transformation Process of the Magnetron-Sputtered Ag2O Film in Hydrogen Annealing

The current paper addresses the effect of the hydrogen partial pressure on the microstructure and transformation of the Ag₂O film. The transformation process and mechanism were also analyzed in detail. Increasing the hydrogen partial pressure can accelerate the transformation of Ag₂O to Ag and lower the critical transformation temperature of the film due to the enhanced hydrogen reduction and to both of the lowered activation energy of the reaction of Ag₂O with hydrogen and enhanced lattice strain of the Ag₂O film. Hydrogen-involved reaction in the whole hydrogen annealing process is mainly hydrogen reduction reaction with Ag₂O. Diffusion of hydrogen and gaseous H₂O molecules accompanies the whole hydrogen annealing process.     

Impact of Extracellular Polymeric Substance in the Inactivation of Harmful Algae by Ag2O/g-C3N4 under Visible Light

Photocatalysis has attracted much attention as an emerging algae removal technology, but the inactivation performance is inevitably affected by the extracellular polymeric substance (EPS) produced by algae. In this study, a photocatalyst (Ag₂O/g-C₃N₄) with efficient algae inactivation is adopted to investigate the interactions with EPS, and the impact of EPS on photocatalytic algae removal is studied. The results show that EPS can adhere to the surface of Ag₂O/g-C₃N₄ by electrostatic force. The interaction with EPS decreases the surface zeta potential of the Ag₂O/g-C₃N₄ from 7.71 to −22.3 mV with the increase in EPS concentration, and the maximum ratio of particle size increases from 825 to 1281 nm. In addition, the interaction with EPS inhibits the release of Ag⁺ in Ag₂O/g-C₃N₄ by half, thus, the toxicity of metal ions will be alleviated. Meanwhile, EPS can also be degraded by Ag₂O/g-C₃N₄, indicating that EPS can work as a radical scavenger to protect the algae cells. Without the protection of EPS, 97.8% of algae cells are inactivated after 5 h photocatalysis. Therefore, more attention should be given to the interaction between EPS and photocatalyst to promote the design and application of the photocatalytic.     

Enhancing the electrical conductivity and thermoelectric figure of merit of the p-type delafossite CuAlO2 by Ag2O addition

(CuAlO₂)_1-x(Ag₂O)_x specimens with 0 ≤ x ≤ 0.06 were prepared through the sintering of mixtures of CuO, Al₂O₃ and Ag₂O powders at 1373 K. Hall effect, Seebeck coefficient and electrical conductivity measurements were subsequently employed to assess the electrical transport properties. The electrical conductivity of the as-sintered samples was found to increase with Ag₂O addition as a result of increases in the carrier density. Over the temperature range of 323–623 K, the transport properties can be attributed to thermally activated transitions from the acceptor state to the valence band. In contrast, the variable range hopping theory is applicable over the temperature range of 623–873 K. Ag₂O addition evidently reduces the defect binding energy in the electronic structure of the CuAlO₂. The addition of this compound also obstructs the formation of both a spinel phase and CuO, such that the oxygen off-stoichiometry value and the carrier density are increased with increasing Ag₂O levels. The presence of Ag metal has the main effect on thermal conductivity below 400 K, while above 400 K increases in the phonon concentration affect the conductivity. The highest value obtained for the figure of merit was 0.0044 at 573 K, from a sample containing 0.2 at.% Ag₂O.     

Microstructure and Optical Properties of AgxO Prepared by Direct-Current Magnetron-Sputtering Method

Two series of AgxO films are prepared on glass substrates by dc magnetron-sputtering method at room temperature and 90℃ under different oxygen to argon gas ratio （OAR） conditions. The mierostrueture is investigated by XRD and SEM in order to obtain the information on the component evolution of AgO＋Ag2O to Ag2O. Its optical properties are investigated by reflectance and absorption spectroscopy to extract the information on metallic and dielectric behaviour evolution of Ag2O, AgO and silver particles and the interband transition. The results indicate that the AgxO film prepared at room temperature is mainly made up of AgO and Ag2 O clusters while Ag2O is the primary component of AgxO prepared at 90℃. The AgxO film mainly consisting of the primary component shows indirect interband transition structure occurring at 2.89eV. Combination of increasing OAR and substrate temperature is an effective method to lower the threshold of thermal decomposition temperature of AgxO and to deal with the bottleneck of short-wavelength optical and magneto-optieM storage.     

The investigation of oxidized silver nanoparticles prepared by thermal evaporation and radio-frequency sputtering of metallic silver under oxygen

The investigation of oxidized silver nanoparticles by the photoemission (XPS, UPS) and HRTEM methods was performed. The nanoparticles of oxidized silver were obtained in the vacuum chamber by two methods of synthesis: thermal evaporation of silver nanoparticles followed by transferring in convective gas flow and sputtering of oxidized clusters under the action of plasma. Both methods indicated that oxygen interaction with silver nanoparticles depends strongly on its size. It was shown that the chemical bonding of oxygen species stabilized on small particles differs from the oxygen species adsorbed on bulk silver surfaces (monocrystals, foils and large particles). The low charged oxygen with molecular type of bonding stabilizes on particles of size approximately 5 nm and smaller. Increasing particle size leads to the dissociation of molecular oxygen species and the formation of strongly charged oxygen composed of oxide nanoparticles like Ag₂O or AgO type. The presence of extended defects in the microdomain large nanoparticles facilitates the formation of Ag₂O or AgO layers covering metallic nanosilver.     

Electrical transport and crystallization in Cu+ ion substituted AgI–Ag2O–V2O5 glassy superionic system

A new glassy solid electrolyte system Cu_xAg_1 − xI–Ag₂O–V₂O₅ has been synthesized. The structural, thermal and electrical properties of the samples have been investigated. The glassy nature of the samples is confirmed by X-Ray diffraction and Differential Scanning Calorimetry studies. The electrical conductivity of these samples increases with CuI content and approaches a maximum value of ∼ 10⁻² Ω^− 1 cm^− 1 for x = 0.35 at room temperature. Ionic mobility measurements suggest that enhancement in the conductivity with Cu⁺ ion substitution may be attributed to increase in the mobility of Ag⁺ ions. The electrical conductivity versus temperature cycles carried out at well-controlled heating rate above T_g and T_c reveal interesting thermal properties. For lower CuI content samples conductivity exhibits anomalous rise above T_g and subsequent fall at T_c. It is also found that CuI addition into AgI–Ag₂O–V₂O₅ matrix reduces the extent of crystallization.     

Preparation of amorphous films of superionic conducting glasses in systems AgIAg2MoO4 and AgIAg2OB2O3

Thermal evaporation, flash evaporation and rf-sputtering techniques were applied to the preparation of amorphous films of superionic conducting glasses in the systems AgIAg₂MoO₄ and AgIAg₂OB₂O₃. The flash-evaporated films were amorphous and showed very high conductivities, about 2 × 10^?2S/cm for the AgIAg₂MoO₄ and about 5 × 10^?3S/cm for the AgIAg₂OB₂O₃ at room temperature, and gave a Ag⁺ transport number of unity. The thermal evaporation method produced crystalline-phase included films. The rf-sputtered films were amorphous by X-ray diffraction and the transport number of Ag⁺ ions was smaller than unity (about 0.9). Thus flash evaporation was concluded to be the most suitable method for preparing amorphous films of superionic conducting glasses.     

Silver-tracer diffusion in Cu2O

The diffusion of¹¹⁰Ag in Cu₂O has been measured by a serial-sectioning technique as a function of temperature (700–1132°C) and oxygen partial pressure (6 × 10^?6 ?8 × 10^?2 atm). The data are fit to the defect model for Cu₂O developed by the authors in the preceding paper. Silver ions have a larger impurity-vacancy binding free energy and/or a larger jump frequency for the singly charged cation vacancies relative to that for the neutral cation vacancies. The activation enthalpies for the diffusion of copper and silver ions in Cu₂O are nearly equal, but the absolute value of D¹_Ag is about three times larger than D¹_Cu even though the silver ion is 31% larger than the copper ion.     

Ag2O nanoparticle clusters coated with porous gelatin-g-PMMA copolymer

Herein a special nanoparticle cluster coated with a porous copolymer is designed and prepared. At first, Ag₂O nanoparticles (secondary particles) were fabricated in gelatin solution by a facile chemical approach. Then these nanoparticles were entrapped in a copolymerization system containing gelatin, methyl methacrylate (MMA), an initiator, and using water as a solvent. The nanoparticle clusters coated with porous gelatin-g-PMMA copolymer (Ag₂O/gelatin-g-PMMA) were prepared by grafting methyl methacrylate onto gelatin, followed by coating solidification. One significant feature for our approach is that every Ag₂O aggregated cluster has been coated with porous gelatin-g-PMMA copolymer film in a unique way, and the Ag₂O nanoparticle could penetrate and escape from the coating freely in water by ultrasonication. As a result, this study provides a new approach to prepare monodispersed nanoparticles by ordered porous copolymers with controlled releasing.     

Improvement of anti-oxidation capability and tribological property of arc ion plated Ag film by alloying with Cu

Ag-Cu alloy film was deposited by arc ion plating (AIP). Atomic oxygen (AO) irradiation experiments were conducted using a ground AO simulation facility. The structure, morphology, composition and tribological property of the Ag-Cu alloy film before and after AO irradiation were investigated and compared with Ag film using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscope (XPS) and ball-on-disk tribometer, respectively. In depth XPS analysis clearly shows that the affected thickness of Ag-Cu alloy film was greatly reduced and the oxidation product was mainly Ag₂O, but AgO and Ag₂O in case of pure Ag film. As a result, the Ag-Cu alloy film exhibited better AO resistant behaviors, and showed a stable friction and low wear after the AO irradiation. The AO resistant behaviors of the Ag-Cu alloy film were discussed in terms of the film microstructure.     

Adsorption behavior of H2O on clean and oxygen precovered Ni(s)(111)

Photoelectron spectroscopy (UPS), thermal desorption spectroscopy (TDS), isotope exchange experiments, work function change (δφ) and LEED were used to study the adsorption and dissociation behavior of H₂O on a clean and oxygen precovered stepped Ni(s)[12(111) × (111)] surface. On the clean Ni(111) terraces fractional monolayers of H₂O are adsorbed weakly in a single adsorption state with a desorption peak temperature of 180 K, just above that of the ice multilayer desorption peak (T_m = 155 K). In the angular resolved UPS spectra three H₂O induced emission maxima at 6.2, 8.5 and 12.3 eV below E_F were found for θ ≈ 0.5. Angular and polarization dependent UPS measurements show that the C_2v symmetry of the H₂O gas-phase molecule is not conserved for H₂O(ad) on Ni(s)(111). Although the Δφ suggest a bonding of H₂O to Ni via the negative end of the H₂O dipole, the O atom, no hints for a preferred orientation of the H₂O molecular axes were found in the UPS, neither for the existence of water dimers nor for a long range ordered H₂O bilayer. These results give evidence that the molecular H₂O axis is more or less inclined with respect to the surface normal with an azimuthally random distribution. H₂O adsorption at step sites of the Ni(s)(111) surface leads in TDS to a desorption maximum at T_m = 225 K; the binding energy of H₂O to Ni is enhanced by about 30% compared to H₂O adsorbed on the terraces. Oxygen precoverage causes a significant increase of the H₂O desorption energy from the Ni(111) terraces by about 50%, suggesting a strong interaction between H₂O and O(ad). Work function measurements for H₂O+O demonstrate an increase of the effective H₂O dipole moment which suggests a reorientation of the H₂O dipole in the presence of O(ad), from inclined to a more perpendicular position. Although TDS and Δφ suggest a significant lateral interaction between H₂O+O(ad), no changes in the molecular binding energies in UPS and no “isotope exchange” between ¹⁸O(ad) and H₂¹⁶O(ad) could be observed. Also, dissociation of H₂O could neither be detected on the oxygen precovered Ni(s)(111) nor on the clean terraces.     

Impedance and Modulus studies of the solid electrolyte system 20CdI2–80[xAg2O–y(0.7V2O5–0.3B2O3)], where 1 ≤x/y ≤ 3

In the present work, an evaluation of the transport properties of super ion conducting quaternary system 20CdI₂–80[xAg₂O–y(0.7V₂O₅–0.3B₂O₃)], where 1 ≤ x/y ≤ 3, in steps of 0.25, to study the effect of changing the modifier to former ratio on the conduction phenomena has been undertaken. Electrical conductivity measurements were made using complex impedance method. The electrical conductivity and conductivity relaxation of the system were studied in the temperature range from 303 K to 333 K and in the frequency range from 100 Hz to 10 MHz. The highest conductivity at room temperature is obtained for the system with modifier to former ratio 1.75. Impedance and modulus analyses had indicated the temperature independent distribution of relaxation times and the non-Debye behavior in these materials. The co-operative motion due to strong coupling between the mobile Ag⁺ ions is assumed to give rise to non-Debye type of relaxation. The silver ionic transport number (t_Ag+) obtained by the emf technique suggested the occurrence of silver ion conduction in the CdI₂-doped Ag₂O–V₂O₅–B₂O₃ system.     

Electrical properties of a new Ag+ ion conducting glassy system: x[0.75AgI:0.25AgCl] : (1−x)[Ag2O : P2O5]

A new fast Ag⁺ ion conducting glassy system: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅], where 0.1 ≤ x ≤ 1 in molar weight fraction, has been synthesized by melt-quench technique using a high-speed twin roller-quencher. An alternate host salt: ‘quenched [0.75AgI: 0.25AgCl] mixed system/ solid solution’, has been used in place of the traditional host AgI. The compositional dependence conductivity studies on the glassy systems: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅] as well as xAgI: (1−x)[Ag₂O: P₂O₅] prepared identically, indicated that the composition at x=0.75 exhibited the highest room temperature conductivity. The composition: 0.75[0.75AgI: 0.25AgCl]: 0.25[Ag₂O: P₂O₅] has been referred to as optimum conducting composition (OCC). The study also revealed that the new/ alternate host yielded better electrolyte system. The activation energy (E_a), involved in the thermally activated conductivity process has been computed from ‘log σ − 1/T’ Arrhenius plot. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.