Effects of excess Te on the thermoelectric properties of p-type 25% Bi2Te3-75% Sb2Te3 single crystal and hot-pressed sinter

Effects of excess Te on the thermoelectric properties of p-type 25% Bi₂Te₃-75% Sb₂Te₃ single crystal and hot-pressed sinter were characterized and understood with the micro-phase diagram near the stoichiometric composition obtained by measuring the equilibrium Seebeck coefficient. Thermoelectric properties of the 25% Bi₂Te₃-75% Sb₂Te₃ single crystal were varied with the amount of excess Te, as -phase of the single crystal becomes less Te-deficient with adding more excess Te. However, thermoelectric properties of the hot-pressed sinter were not varied with the amount of excess Te, because the composition of -phase is not changed with the amount of excess Te. While a maximum figure-of-merit of 2.39 × 10^–3/K at 300 K was obtained for the 25% Bi₂Te₃-75% Sb₂Te₃ single crystal by adding 6 wt % excess Te, the hot-pressed 25% Bi₂Te₃-75% Sb₂Te₃ sinter exhibited the figure-of-merit of 2.97 × 10^–3/K regardless of the excess Te amount.     

Converting ultrafine silver nanoclusters to monodisperse silver sulfide nanoparticles via a reversible phase transfer protocol

To achieve better control of the formation of silver sulfide (Ag₂S) nanoparticles, ultrasmall Ag nanoclusters protected by thiolate ligands (Ag₄₄(SR)₃₀ and Ag₁₆(GSH)₉) are used as precursors, which, via delicate chemistry, can be readily converted to monodisperse Ag₂S nanoparticles with controllable sizes (4–16 nm) and switchable solvent affinity (between aqueous and organic solvents). This new synthetic protocol makes use of the atomic monodispersity and rich surface chemistry of Ag nanoclusters and a novel two-phase protocol design, which results in a well-controlled reaction environment for the formation of Ag₂S nanoparticles.

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Room temperature interactions in Ag-metals thin film couples

The results of room temperature interactions of silver and various metals in thin films are presented. It has been found that aluminium, gold, bismuth, chromium, copper, antimony and samarium do not react with silver under the conditions given, but cadmium, gallium, indium, tin, tellurium and zinc do, and the reactions lead to the formation of corresponding intermetallic compounds. In the AgGa system only one compound is formed, which has been identified as Ag₃Ga. In the AgIn system, with less than 50 wt.% In, one compound is formed and this has been identified as Ag₂In. A compound formed with over 50 wt.% In has been identified as AgIn₂ LT (low temperature phase). Between 60 and 120°C this compound transforms into AgIn₂ MT (medium temperature phase). In the AgSn system the compound Ag₃Sn is formed and in the AgTe system the compounds Ag₂Te and Ag₅Te₃ are formed.     

Controlled Synthesis of Ag2Te@Ag2S Core–Shell Quantum Dots with Enhanced and Tunable Fluorescence in the Second Near‐Infrared Window

Fluorescence in the second near‐infrared window (NIR‐II, 900–1700 nm) has drawn great interest for bioimaging, owing to its high tissue penetration depth and high spatiotemporal resolution. NIR‐II fluorophores with high photoluminescence quantum yield (PLQY) and stability along with high biocompatibility are urgently pursued. In this work, a Ag‐rich Ag₂Te quantum dots (QDs) surface with sulfur source is successfully engineered to prepare a larger bandgap of Ag₂S shell to passivate the Ag₂Te core via a facile colloidal route, which greatly enhances the PLQY of Ag₂Te QDs and significantly improves the stability of Ag₂Te QDs. This strategy works well with different sized core Ag₂Te QDs so that the NIR‐II PL can be tuned in a wide range. In vivo imaging using the as‐prepared Ag₂Te@Ag₂S QDs presents much higher spatial resolution images of organs and vascular structures as compared with the same dose of Ag₂Te nanoprobes administrated, suggesting the success of the core–shell synthetic strategy and the potential biomedical applications of core–shell NIR‐II nanoprobes.     

Ga as an additive in the As2Te3 glass

Results of measurements of the mean atomic volume (V), the glass transition temperature (T _g), the activation energy for glass transition (E _t) and the d. c. electrical conductivity () are reported and discussed for ten glass compositions of the Ga–As–Te system. The glasses studied can be represented as Ga _x (As_0.4Te_0.6)_100–x glasses, with the additive Ga ranging from 0 to 12 atomic percent (at.%) in the parent As₂Te₃glass. In the Ga _x (As_0.4Te_0.6)_100–x glasses, changes in slope are observed in the V, T _g, E _t, and other electronic properties, at the composition with a Ga content of 2 at.%. The results are compared with those obtained on introduction of Ag and Cu to the As₂Te₃and the [0.5As₂Te₃–0.5As₂Se₃] glasses. Analysis of the data suggest formation of GaAs, Ga₂Te₃and excess Te structural units (s.u.) in lieu of some of the original As₂Te₃s.u., for addition of Ga up to 2 at.% to the parent As₂Te₃glass; for higher Ga contents, formation of GaAs, GaTe and excess Te s.u. are indicated.     

Use of metastable, dissociated and charged gas species in synthesis: a low pressure analogue of the high pressure technique

Oxidation of silver using microwave-induced oxygen plasma and oxygen-ozone gas mixture was studied as a function of temperature and partial pressure. The oxide Ag₂O was formed at temperatures well above its normal decomposition temperature in oxygen plasma at a pressure of 5 Pa. The higher oxide AgO_1–x was formed in O₂₊O₃ gas mixtures at lower temperatures. The oxygen chemical potentials for the oxidation of Ag to Ag₂O, Ag₂O to AgO_1–x and AgO to Ag₂O₃ were evaluated from thermodynamic data and compared with the experimental results to obtain information on the chemical potential of oxygen in microwave plasma and gases containing ozone. The oxygen potential of the gas phase in microwave plasma operating at a pressure of 5 Pa was found to be in excess of 36 kJ/mol at 750 K. This is equivalent to a pressure of diatomic oxygen gas greater than 3 × 10⁷ Pa. In the O₂₊O₃ mixture at ambient pressure containing 5 mole percent O₃, the oxygen potential is 112 kJ/mol at 465 K. The equivalent pressure of diatomic oxygen is 4 × 10¹⁷ Pa. Thus, metastable species such as O₃ or charged species such as O^– present in plasma can be used as a powerful reagent for the syntheses of metastable oxides. Similar techniques can be used for other metastable inorganic solids such as nitrides for functional applications.     

AES and XPS study on the tarnishing of silver in alkaline sulphide solutions

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to follow the changes that occur on the surfaces of silver sheets when reacting with sulphide solutions of pH 12. The results obtained enabled conclusions to be drawn about the nature of the Ag₂S films. Immersion in dilute sulphide solutions ( 3 × 10^–4 M) resulted in highly irregular films that were interrupted by shallow depressions (cavities). Inside these cavities AES analysis proved the existence of massive carbon species, the presence of which delayed healing of the cavities by the formation of Ag₂S film, thus allowing the silver metal interface to continue in contact with the solution oxygen. This explains why silver electrodes maintain the Ag/Ag₂O potential while immersed in dilute sulphide solutions. Equilibration of silver with more concentrated sulphide solutions (5 × 10^–4 to 5 × 10^–3 M) effected healing of the cavities through the formation of a continuous Ag₂S film. Once this continuous film is formed, the metal interface is no longer accessible to the solution oxygen. At this point the transition of potential from Ag/Ag₂O to Ag/Ag₂S occurs.     

Phase diagram and thermoelectric properties of Ag3−x Sb1+x Te4 system

In order to obtain better thermoelectric performance in the composition domain should be stabilized, the phase diagram of the Ag_3–x Sb_1+x Te₄ system by varying the Ag:Sb ratio. The phase diagram is investigated using the differential thermal analysis and the powder X-ray diffraction techniques. The Seebeck coefficient and the electrical resistivity of the grown bulk crystals of the system are also measured. The phase diagram of the Ag_3–x Sb_1+x Te₄ system indicates that a mixed phase of AgSbTe₂ and Ag₂Te, which is expected to show higher thermoelectric performance, exists in a wide temperature range between 600 and 830 K at a composition of Ag_2.2Sb_1.8Te₄. The maximum of Seebeck coefficient for AgSbTe₂ (x = 1) is 0.73 mV/K at about 680 K. The thermoelectric performance is lowered by the compositional deviation from Ag:Sb:Te = 1:1:2.     

Metal-nonmetal transition and the electronic transport behavior in disordered PbO<Subscript>2</Subscript>-Ag<Subscript>2</Subscript>O-xCsystem synthesized by ball milling

The electronic transport properties as a function of temperature and the graphite content have been investigated for disordered PbO₂-Ag₂O-xC (0 x 3) composite materials. The components of the system change from (1) lead-silver oxides of Ag₅Pb_2.5O₆ and/or Ag₂PbO₂ to (2) PbCO₃ + 2PbCO₃PbO + Ag and (3) PbCO₃ + Ag + Pb with increasing the graphite content. Ag₅Pb₂O₆ is synthesized directly by mechanical milling with a simple solid-state reaction of Ag₂O and PbO₂. The structure, thermal and electric properties of silver-lead oxides are characterized by means of X-ray diffraction, scanning electron microscope, a differential scanning calorimeter analysis and DC resistivity measurements. Strengthening the degree of disorder through mechanical milling and/or doping the lead oxide into Ag₅Pb₂O₆ causes the conductivity transition from metallic to semiconducting behavior, while decreasing the degree of disorder by annealing and the segregation of the lead oxide from the solid solution leads to a reverse transition.     

Dissolution kinetics and diffusivity of silver in glassy layers for hybrid microelectronics

Silver and palladium/silver compositions are widely used in hybrid microelectronics, as electrodes for dielectric layers and multilayers, terminations of thick film resistors and interconnections. Interactions between Ag and the adjacent films are known to affect the microcircuit performances. The present study is aimed at collecting data on the behavior of Ag-based films in contact with glassy layers. Most experiments were performed with a glass with composition 68.2 PbO : 30.5 SiO₂ : 1.3 Al₂O₃ wt %. Two different systems were analyzed. The first system consists of thick films prepared from a paste containing glass and either 3 or 15 wt % silver particles; both fine (spherical grains, 0.5–1 m diameter) and coarse (flakes, 2–5 m, <1 m thick) Ag powders were used for these pastes. The distribution of Ag in the film was studied with X-ray diffraction, scanning electron microscopy and fluorescence analysis. The results show that Ag floats on the glassy layer. Diffraction of X-rays generated by a synchrotron radiation source allowed us to study the kinetics of silver dissolution in the glass; this phenomenon is consistent with the Avrami theory, with an apparent activation energy E _dis=0.69±0.04 eV. The second system analyzed, Ag-based terminations of glass layers fired at various peak temperatures, enabled us to obtain quantitative values for both Ag solid solubility (about 2.5 wt %) and Ag diffusion coefficients D _Ag(T ). Typical values of D _Ag(850 °C) are 30.3±11.9 10^–8 cm²/s; an apparent activation energy of the diffusion process is E _a=0.6±0.1 eV.     

Synthesis of Ultrathin Topological Insulator β-Ag2Te and Ag2Te/WSe2-Based High-Performance Photodetector

β-Ag₂Te has attracted considerable attention in the application of electronics and optoelectronics due to its narrow bandgap, high mobility, and topological insulator properties. However, it remains a significant challenge to synthesize 2D Ag₂Te because of the non-layered structure of Ag₂Te. Herein, the synthesis of large-size, ultrathin single crystal topological insulator 2D Ag₂Te via the van der Waals epitaxial method for the first time is reported. The 2D Ag₂Te crystal exhibits p-type conduction behavior with high carrier mobility of 3336 cm² V⁻¹ s⁻¹ at room temperature. Taking advantage of the high mobility and perfect electron structure of Ag₂Te, the Ag₂Te/WSe₂ heterojunctions are fabricated via mechanical stacking and show an ultrahigh rectification ratio of 2 × 10⁵. Ag₂Te/WSe₂ photodetector also exhibits self-driven properties with a fast response speed (40 µs/60 µs) in the near-infrared region. High responsivity (219 mA W⁻¹) and light ON/OFF ratio of 6 × 10⁵ are obtained under the photovoltaic mode. The overall performance of the Ag₂Te/WSe₂ photodetector is significantly competitive among all reported 2D photodetectors. These results indicate that 2D Ag₂Te is a promising candidate for future electronic and optoelectronic applications.     

Silver solubility in PbTe crystals

Silver solubility in lead telluride single crystals has been determined using electron microscopy, x-ray microanalysis, microhardness tests, and hydrostatic density measurements. The results indicate that the limit of the Pb_{1 ? x} Ag _x Te solid-solution series is near x = 0.006. With increasing silver content, the density of the Pb_{1 ? x} Ag _x Te solid solutions drops, while their microhardness rises.     

Influence of silver addition on microstructures and transport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>:Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> composites

In order to obtain high temperature coefficient of resistance (TCR) value of La_0.67Ca_0.33MnO₃:Ag _x (LCMO:Ag _x ) composites, samples with different Ag contents (x?=?0, 0.1, 0.2, 0.25, 0.3, and 0.5) were prepared by sol–gel method. X-ray diffraction analyses indicated that all samples had orthorhombic perovskite structures. As x increased, lattice parameters (a, b, c) and cell volumes underwent slight expansions. Interestingly, the addition of Ag dramatically affected TCR and magneto-resistance (MR) values. Elevated TCR value up to 53.46%·K^?1 at 277 K was observed for LCMO:Ag _x composites with added Ag at the composition of x?=?0.1. Meanwhile, MR value at 263 K reached 71% at the magnetic field of 1 T for samples with Ag composition of x?=?0.25. The increase in Mn⁴⁺/Mn³⁺ ratio and improvement in crystallization caused by added Ag was found responsible for the elevated values of TCR, MR, and T_p. These findings may have practical use in high-performance magneto-resistive manganites.     

Photogeneration of Donor Pairs in ZnSe{Ag} Crystals

Experimental evidence is presented that photoinduced defect reactions in ZnSe{Ag} crystals give rise to the formation of (Ag⁰ _i)₂ interstitial donor pairs. As a result, the induced impurity photoconductivity spectrum shows, along with the band at 0.29 eV due to isolated Ag⁰ _i atoms, a series of narrow bands in the range 0.3–0.6 eV (quasi-line spectrum). The energy positions and relative intensities of these bands are accounted for in terms of different pair separations in (Ag⁰ _i)₂. The charge instability of Ag_i under band-gap excitation, associated with multiple electron trapping processes, leads to atomic instability, which gives rise to ionization-enhanced diffusion and the formation of (Ag⁰ _i)₂ donor pairs.     

Preparation and photovoltaic properties of anodically grown Ag2O films

The semiconducting and photovoltaic properties of p-type Ag₂O films grown anodically on silver electrodes were studied, in view of possible applications in solar energy conversion. Films were grown in different alkaline solutions; the best results were obtained for 0.02M Ag₂SO₄ + 0.17M NH₄OH + 5.7 × 10^–3M Ba(OH)₂ saturated with Ag₂O powder, stirred mechanically at room temperature. Film thicknesses of up to 10m were thus obtained for the first time in anodically grown Ag₂O. Photovoltaic spectra taken at 300 K give a bandgap ofEg = 1.42 ± 0.04 eV. Evaporated gold on Ag₂O appears to be ohmic while aluminium and platinum are rectifying. The barrier height of Ag/Ag₂O is 0.90 ± 0.02 eV, that of Al/Ag₂O is 0.93 ± 0.02 eV, and that of platinum 0.94 ± 0.02 eV. The best cells give an open-circuit voltage,V _oc, of over 150 mV, and a short circuit current,I _sc = 100A cm^–2 under 50 mW cm^–2 illumination.     

Plasmonic effect and bandgap tailoring of Ag/Ag2S doped on ZnO nanocomposites for enhanced visible-light photocatalysis

Ag/Ag₂S-ZnO nanocomposites were prepared via a simple hydrothermal process followed by a plasmonic Ag⁺ reduction through a photo-deposition method. Ag₂S was introduced to narrow the overall composite bandgap and activate the surface plasmon resonance (SPR) effect of the Ag⁺ cation present. The physicochemical properties of the as-synthesised catalysts were characterised by X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), Brunauer-Emmett-Teller (BET) analysis. Fourier-transform infrared spectroscopy (FTIR), Ultraviolet diffuse reflectance spectroscopy (UV–vis DRS), photoluminescence emission spectra (PL) and X-ray photoelectron spectroscopy (XPS) was conducted to investigate the photo-absorption and emission spectra of the nanocomposites. The degradation efficiency of all the synthesised catalysts (ZnO, Ag₂S, Ag/ZnO and Ag₂S/ZnO) prior to the final product, Ag/Ag₂S/ZnO was tested and compared. Results showed that the ternary Ag/Ag2S/ZnO achieved a 98 % phenol removal compared to 50 %, 11 %, 64 % and 93 % for ZnO, Ag2S, Ag/ZnO and binary Ag2S/ZnO, respectively. The degradation kinetics followed the Langmuir-Hinshelwood model, which typically describes heterogeneous photocatalytic surface reactions. The linear fits had R² values higher than 0.97, which confirms the degree of accuracy or statistical fitness to the kinetic model. Degradation scavenger test confirmed the holes (h⁺) as the main inhibitor and identified the superoxide O₂?¯ radical as the main active specie responsible for the degradation. Total organic carbon analysis using the ternary Ag/Ag₂S-ZnO catalyst only achieved a 74% phenol mineralization after 24 h of photocatalysis. Recyclability tests showed good phenol removal stability of Ag/Ag₂S-ZnO at 41 % after five recycle runs. Hence, a synergistic degradation mechanism responsible for the efficient photo-degradation performance was proposed.     

Epitaxial growth and reaction between Ag and SnTe substrates

The vacuum deposition of silver on thin film SnTe substrates at temperatures between 110 K and 620 K was studied by transmission electron microscopy and diffraction. It was found that at temperatures up to 370 K silver deposits grow in nearly perfect (001)[100]Ag//(001)[110]SnTe orientation. At higher substrate temperatures a topotactic exchange of Sn and Ag atoms between the substrate and deposit takes place leading to two perfectly oriented reaction products: Ag₂Te and Ag₃Sn. Their orientation relations were determined, and possible formation mechanisms are briefly discussed.     

Microstructure, topology and X-ray diffraction in Ag-metal reinforced polymer of polyvinyl alcohol of thin laminates

A polymer composite of Ag-metal reinforced polyvinyl alcohol (PVA) is synthesized in shape of thin laminates of 200–300 μm thickness. The process involves a chemical Ag⁺ dispersion in PVA and in-situ reduction-reaction with active PVA molecules under hot conditions (with stirring) in water at 60–70°C temperature. The product results in a metal Ag-polymer complex dispersed in the solution. After evaporating part of water, a derived viscous solution is casted (in hot conditions) in shape of a thin laminate in a glass mould. In addition to chemical reducer, active OH-groups (free from H-bonding) in PVA molecules of refreshed surfaces act as head groups to adsorb Ag⁺ and drive a directional growth. Short fibrils of Ag-metal thus occur in reaction over the PVA molecules. Casting thin laminates from a liquid sample Ag-PVA allows the fibrils (also the polymer molecules) to align along the surface. Selected Ag-contents up to 5.0 wt.% in Ag-PVA laminates are studied in terms of scanning electron micrograph, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. Average size, morphology and aspect ratio (ϕ) vary in Ag-metal depending on the Ag-content. As long Ag-metal fibrils as 2–5 μm, ϕ=35, occur in a sample of 2.0 wt.% Ag. The Ag-metal reflects in two characteristic 3d_5/2 and 3d/_3/2 XPS bands of 368.3 and 374.1 eV respectively.     

Low-temperature magnetic and electromagnetic studies of Y-Ba-Cu-O: Agx Ceramic superconductor

Magnetization and magnetic relaxation measurements have been studied at 4.2 K on YBa₂Cu₃O_7–:Ag _x (x=0 to 1.2) superconducting samples prepared by a coprecipritation technique. Remanent magnetization and hysteresis loops were found to be increased on Ag addition. Transport current density (J _c) was enhanced with the addition of Ag concentration. Flux creep rate was also increased with increase in Ag addition resulting in stronger pinning potential. Microwave-induced d.c. voltage measurements show a reduction of weak links with increase in Ag concentration. The enhancement of transportT _c is attributed to the stronger Josephson current paths due to the reduction of the total number of weak links after Ag addition.     

Ultrasmall Ag+-rich nanoclusters as highly efficient nanoreservoirs for bacterial killing

Metallic silver （Ag） and its ability to combat infection have been known since ancient history. In the wake of nanotechnology advancement, silver＇s efficacy to fight broad spectrum bacterial infections is further improved in the form of Ag nanoparticles （NPs）. Recent studies have ascribed the broad spectrum antimicrobial properties of Ag NPs to dissociation of Ag＊ ions from the NPs, which may not be entirely applicable when the size of Ag NPs decreases to the sub-2 nm range [denoted Ag nanoclusters （NCs）]. In this paper we report that ultrasmall glutathione （GSH）-protected Ag^＋-rich NCs （Ag^＋-R NCs for short, with a predominance of Ag＋ species in the NCs） have much higher antimicrobial activities towards both gram-negative and gram-positive bacteria than the reference NC, GSH-Ag^＋-R NCs. They have the same size and surface ligand, but with different oxidation states of the core silver. This interesting finding suggests that the undissociated Ag^＋-R NCs armed with abundant Ag^＋ ions on the surface are highly active in bacterial killing, which was not observed in the system of their larger counterpart, Ag NPs.