Copper ion-selective chalcogenide glass electrodes: Analytical characteristics and sensing mechanism

New copper ion-selective electrodes based on chalcogenide glasses, Cu_xAg_25?xAs_37.5Se_37.5, display high copper(II) ion sensitivity with Nernstian response in the range pCu 1–6, short response time, high selectivity, potential stability and reproducibility. These electrodes are 10–30 times more sensitive in strongly acidic media than crystalline copper ion-selective sensors and are superior to the copper(I) selenide electrode in selectivity and resistance to acids and oxidation. A model is proposed to explain the ion sensitivity of these chalcogenide glass sensors. The sensitivity depends on direct exchange of copper(II) ions between solution and the modified surface layer of the glass. The modified surface layer is formed as a result of partial destruction of the glass network on soaking in solution; its atomic density is 2.0–2.5 times less than that of the original glass. The structural defects and hollows make fast copper(II) ion migration within the modified surface layer possible. Exchange sites in this layer can be formed by both disproportionation and oxidation of copper(I) in the glass network, as well as by diffusion of copper(II) ion from solution in the case of glasses with low copper content. Experimental confirmation of this model is provided by x-ray, photo-electron and scanning Auger electron spectroscopy.     

Laser desorption ionization time‐of‐flight mass spectrometric study of binary As‐Se glasses

Binary chalcogenide As‐Se glasses and their thin films are important for optics, computers, materials science and technological applications. To increase understanding of the properties of thin films fabricated by plasma deposition techniques, more information concerning the physics of plasma plume is needed. In this study the formation of clusters in plasma plume from different As‐Se glasses by laser desorption ionization (LDI) or laser ablation (LA) was studied by time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. Formation of a number of As_pSe_q singly charged clusters As₃Se (q = 1–5), AsSe (q = 1–3), As₂Se (q = 2–4), and As₃Se (q = 2–5) was found from As‐Se glasses with the molar ratio As:Se in the range from 1:2 to 7:3. The stoichiometry of the As_pSe_q clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is proposed and the relationship to the structure of the parent glasses, as also suggested by Raman scattering spectra, is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Large optical Kerr effect in bulk GeSe2–In2Se3–CsI chalcohalide glasses

Third-order nonlinear optical properties of GeSe₂–In₂Se₃–CsI chalcogenide bulk glasses are studied by Standard pico-second (ps) time-resolved optical Kerr effect (OKE) technique. The obtained χ⁽³⁾ and n₂ at 1064 nm of the glass 72.25GeSe₂–23.75In₂Se₃–5CsI are as large as 10.07 × 10⁻¹² esu and 6.5 × 10⁻¹⁸ m²/W, respectively, more than twice that of As₂S₃ glass. The relationship between glass compositions and the third-order nonlinear optical responses was analyzed by Raman spectra in terms of structural evolution. It is suggested that the tetrahedral units ([GeSe₄] and [InSe₄]) play an important role in the ultrafast third-order nonlinear optical responses of these chalcohalide glasses.     

Effect of γ-irradiation exposure on optical properties of chalcogenide glasses Se70S30−xSbx thin films

We investigate in the present paper the effect of the γ-irradiation exposure by 100–500 kGy doses on the optical properties and single oscillator parameters for chalcogenide glasses Se₇₀S_30?xSb_x (x=0, 12, 18 and 30 at%) thin films. These parameters were modeled from transmission spectra data measured by spectrophotometry in the wavelength range 200–2500 nm. It was found that the refractive index of the investigated films increases with increasing the doses of γ-radiation. This post-irradiation increase in the refractive index was interpreted in terms of the increase of the density of the investigated films with irradiation due to ionization or atomic displacements. Besides, the refractive index dispersions data of both the as-deposited and γ-irradiated Se₇₀S_30?xSb_x films obeyed the single oscillator model. The calculated single oscillator parameters; oscillator strength E_d, static refractive index n_o, zero frequency dielectric constant ε_o increased after irradiation while the oscillator energy E_o, reduced after irradiation. The absorption coefficient was found to increase with the increase of the doses of γ-radiation. Furthermore, the obtained optical energy gap of chalcogenide glasses Se₇₀S_30?xSb_x films was found to decrease with increasing the doses of γ-radiation which is attributed to increase of the defects after irradiation. This is confirmed by the decrease in the Urbach energy E_e after radiation. The γ-irradiation stimulated increase in the absorption coefficient and change in the optical parameters which can be utilized for industrial dosimetric purposes.     

The kinetics of phase transitions in vitreous chalcogenide semiconductors As10.2Se89.8 and As9Se90Bi in early stage of physical ageing process

The kinetics of glass transition in selenide glasses As_10.2Se_89.8 and As₉Se₉₀Bi in early stage of physical ageing process has been investigated by parallel differential scanning calorimetry (DSC) and exoelectron emission (EEE). It has been found that the glass transition process occurring in investigated glasses is evidenced by peaks on EEE intensity and DSC curves. Admixture of bismuth causes a distinct lowering of the temperature of glass transitions process both in the surface layer and in the volume. The addition of Bi causes a decrease in the value of the activation energy for glass transition process in both the volume and in the surface layer, thus reducing the thermal stability of investigated glasses. Physical ageing in Se-rich chalcogenide glasses leads to a significant increase of endothermic peak area A, temperature of glass transition T _g and decrease of the activation energy value E. All these effects are strongly dependent on glass composition.     

New Sensory Materials Based on Chalcogenide Glasses Containing Zinc,Cadmium, and Manganese Sulfides

New chalcogenide glasses of the system 0.5AgI-(0.5 - x)Sb₂S_3-x MS containing cadmium, man- ganese, and zinc sulfides were obtained. The high purity of these materials and their glassy state were proved by X-ray analysis and X-ray fluorescence energy-dispersive spectroscopy. The impedance of the glasses obtained was measured within a wide range of frequencies, and the dependences of the conductivity on the composition of glasses were studied. New potentiometric sensors based the new glasses were developed, and an electrochemical experiment was carried out.     

Thermoanalysis of quasi-ternary As2(S,Se, Te)3 semiconductor glasses

In comparison with other chalcogenide glassy systems, less attention has been paid to the quasi-ternary (quaternary) system As₂(S, Se, Te)₃. In this paper, thermal methods were used to characterize ten different quaternary homogenous semiconductor glasses that were prepared by mixing the stoichiometric binary systems As₂S₃, As₂Se₃ and As₂Te₃. The ratios of the constituent binaries in the quasi-ternary glasses exerted a great influence on their thermal spectrum. The samples poor in As₂Te₃ showed neither the exothermic nor the endothermic peak due to crystallízation (T _c) and melting (T _m), respectively, but only the glass transition (T _g). Three transition temperatures,T _g, T_c andT _m, were detected for other compositions. On the other hand, a phase separation was observed in the samples rich in As₂Te₃. A cyclic scanning technique was used to investigate the thermally-induced phases during two consecutive heat ing-cooling cycles covering the temperature rangeT _g?T_m. The energy of decompositionE _d decreased on increase of the ratio As₂S₃/As₂Se₃ (at constant As₂Te₃), whereas it increased on increase of the ratio As₂Te₃/As₂Se₃ (at constant As₂Se₃ or As₂S₃).     

Crystallization Kinetics of Pb20Ge17Se63 and Pb20Ge22Se58 Chalcogenide Glasses

Two glasses of the chalcogenide system Pb₂₀Ge_xSe_80-x, with x =17 and 22 at.%, were prepared by the melt quench technique. Differential scanning calorimetry emphasized that the investigated Pb₂₀Ge₁₇Se₆₃ and Pb₂₀Ge₂₂Se₅₈ glasses are crystallized to GeSe₂ and PbSe₂ as well as GeSe₂ and PbSe, respectively as revealed by X-ray diffraction analysis. It was found that the glass transition temperatures of the Pb₂₀Ge₂₂Se₅₈ glass are higher than those of Pb₂₀Ge₁₇Se₆₃ ones. The respective values for the activation energy of glass transition (E _t ) for Pb₂₀Ge₁₇Se₆₃ and Pb₂₀Ge₂₂Se₅₈ are found to be 434±20 and 761±77 kJ mol^-1, while those for the annealed samples are 928±85 and 508±23 kJ mol^-1, respectively. The activation energies of crystallization (E _c) before and after annealing were determined using different methods. Applying the modified Johnson-Mehl-Avrami (JMA) equation, it could be found that GeSe₂ is crystallized by surface crystallization, while both PbSe₂ and PbSe are crystallized by bulk crystallization in three dimensions . This revised version was published online in August 2006 with corrections to the Cover Date.     

Novel synthesis of a highly active carbon-supported Ru85Se15 chalcogenide catalyst for the oxygen reduction reaction

A carbon-supported Ru₈₅Se₁₅ chalcogenide catalyst was synthesized via a microwave-assisted polyol process using RuCl₃ and Na₂SeO₃ as the Ru and Se precursors. The Ru₈₅Se₁₅ chalcogenide catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The XRD pattern for Ru₈₅Se₁₅/C clearly exhibited the characteristic reflections of metallic ruthenium. The TEM image indicated that the Ru₈₅Se₁₅ chalcogenide catalyst was well dispersed on the surface of the carbon support with a narrow particle size distribution. Rotating disk electrode (RDE) and single-cell measurements were carried out to evaluate the electrocatalytic activity of the Ru₈₅Se₁₅ chalcogenide catalyst. The oxygen reduction reaction (ORR) activity of the Ru₈₅Se₁₅/C catalyst was compared with the commercial Pt/C catalyst with the absence/presence of methanol. In the absence of methanol, the Ru₈₅Se₁₅/C catalyst showed a comparable ORR activity with the Pt/C catalyst. However, in the presence of methanol, the Ru₈₅Se₁₅/C catalyst showed a better ORR activity than the Pt/C catalyst. The performance of the membrane electrode assembly (MEA) prepared with Ru₈₅Se₁₅/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) showed the maximum power density of 400 mW cm⁻² at the current density of 1300 mA cm⁻².     

Disordered La3Cu4.88Se7

The crystal structure of copper(I) lanthanum selenide, La₃Cu_4.88Se₇, obtained from the La₂Se₃–Cu₂Se quasi‐binary system, has been investigated using X‐ray single‐crystal diffraction. The positions of the La and Se atoms are ordered and lie on mirror planes, whereas all positions for the Cu atoms are partially occupied. The crystal is built from edge‐sharing [LaSe₆] and [LaSe₇] polyhedra. The five positions for the Cu atoms determine an ionic diffusion pathway in the structure.     

Cs6Nb4Se22 and K12Nb6Se35.3: two new compounds containing the M4Q22 building block

The title compounds, namely hexacaesium tetraniobium docosaselenide and dodecapotassium hexaniobium pentatriacontaselenide, were formed from their respective alkali chalcogenide reactive flux and niobium metal. Both compounds fall into the larger family of solid‐state compounds that contain the M₂Q₁₁ building block (M = Nb, Ta; Q = Se, S), where the metal chalcogenide forms dimers of face‐shared pentagonal bipyramids. Cs₆Nb₄Se₂₂ contains two Nb₂Se₁₁ building blocks linked by an Se—Se bond to form isolated Nb₄Se₂₂ tetrameric building blocks surrounded by caesium ions. K₁₂Nb₆Se_35.3 contains similar Nb₄Se₂₂ tetramers that are linked by an Se—Se—Se unit to an Nb₂Se₁₁ dimer to form one‐dimensional anionic chains surrounded by potassium ions. Further crystallographic studies of K₁₂Nb₆Se_35.3 demonstrate a new M₂Se₁₂ building block because of disorder between an Se²⁻ site (85%) and an (Se—Se)²⁻ unit (15%). The subtle differences between the structures are discussed.     

Kupferchalkogenid‐Clusterverbindungen mit nitro‐funktionalisierter Ligandenhülle

Copper Chalcogenide Cluster Compounds with Nitro‐functionalized Ligand Shell Three new copper chalcogenide cluster molecules, [Cu₄(SC₆H₄NO₂)₄(PPh₃)₄] ( 1 ), [Cu₄(SC₆H₄NO₂)₂(OAc)₂(PPh₃)₄] ( 2 ), and [Cu₂₂Se₆(SC₆H₄NO₂)₁₀(PPh₃)₈] ( 3 ), have been synthesized and characterized by single crystal X‐ray structure analysis. 1 and 2 were prepared from the reactions of Cu(OAc) and HSC₆H₄NO₂ in the presence of PPh₃ and have a similar “chair” structure in which two copper atoms are trigonally coordinated and two are tetrahedrally coordinated. The nitro groups of the ligands are not coordinated to any metal atom, but are located on the surface of the organic shell of the cluster molecules. In a further reaction between 2 and Se(SiMe₃)₂, cluster 3 was crystallized. Crystals of 3 include approximately 16.5 molecules THF per formula unit. This synthesis demonstrates the use of these “small” copper chalcogenide clusters as precursor compounds for the synthesis of bigger species. Non‐functionalized compounds similar to 1 and 2 are typically very pale or even colourless crystals. This is in contrast to the clusters presented in this work, which formed intensively orange or red crystals, due to the presence of the nitro groups. To investigate the influence of these nitro groups on the optical properties in more detail we have carried out UV‐VIS spectroscopic measurements.     

Synthesis,Structural, and Optical Characterization of a New Europium(II) Tin Selenide,Eu8(Sn4Se14)(Se3)2 with a (Sn4Se14)12– Building Block

A new phase in europium‐tin‐chalcogenide chemistry has been prepared using the reactive flux method: Eu₈(Sn₄Se₁₄)(Se₃)₂. The compound crystallizes in the orthorhombic space group P2₁2₁2 with cell parameters a = 11.990(2) Å, b = 16.425(4) Å, c = 8.543(1) Å, and Z = 2. Eu₈(Sn₄Se₁₄)(Se₃)₂ is a three dimensional structure with Eu^II cations linked together with an unusual (Sn₄Se₁₄)^12– anionic unit and (Se₃)^2– chains. UV‐VIS‐NIR band‐gap analysis shows that these black metallic crystals are likely semiconductors with an optical band‐gap of 1.07 eV.     

Synthesis and Crystal Structure of Bis(tetraethylammonium) Octabromo‐triselenate(II)‐{dibromodiselenate(I)}, [NEt4]2[Se3Br8(Se2Br2)], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The brown crystals of [NEt₄]₂[Se₃Br₈(Se₂Br₂)] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraethylammonium bromide. The crystal structure of 1 has been determined by the X‐ray methods and refined to R = 0.0308 for 10433 reflections. The crystals are monoclinic, space group P2₁ with Z = 2 and a = 12.0393(3) Å, b = 11.8746(3) Å, c = 13.1946(3) Å, β = 96.561(1)° (123 K). In the solid state structure the anion of 1 is built up of Se₃Br₈ unit which consists of a triangular arrangement of three planar SeBr₄ units sharing a common edge through two μ₃‐bridging Br atoms, and one Se₂Br₂ molecule which is linked to one of μ₃‐bridging Br atoms. The three Se^II atoms form a triangle which is almost perpendicular to the planes given by three SeBr₄ moieties. The contact between the μ₃Br and the Se^I atom of the Se₂Br₂ molecule is 3.1711(8) Å and can be interpreted as a bond of the donor‐acceptor type with the μ₃Br as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II‐Br and μ₃Br‐Se^II bond lengths are in the ranges 2.3537(7)–2.4737(7) Å and 2.7628(7)–3.1701(7) Å, respectively. The bond lengths in coordinated Se₂Br₂ molecule are: Se^I‐Se^I = 2.2636(9) Å, Se^I‐Br = 2.3387(11) and 2.3936(8) Å.     

Synthesis and characterization of Cu3Se2 nanofilms by an underpotential deposition based electrochemical codeposition technique

The Cu₃Se₂ nanofilms were synthesized with underpotential deposition based electrochemical codeposition technique for the first time in the literature. The electrochemical behaviors of copper and selenium were investigated in 0.1 M H₂SO₄ on Au electrode. The effects of concentration and scan rate on the electrochemical behavior of selenium were studied. The electrochemical behaviors in underpotential deposition and bulk regions of the Cu-Se system were investigated in acidic solution by cyclic voltammetry and electrolysis techniques. X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman spectroscopy, and ultraviolet and visible absorption spectroscopy techniques were used for characterization of synthesized films. According to the X-ray photoelectron spectroscopy spectrum, Cu/Se ratio was determined to be approximately 3/2. Copper selenide nanofilms are two phases and polycrystalline according to X-ray diffraction. The films mainly formed tetragonal Cu₃Se₂ (umangite mineral structure) structure and the particle size was approximately 45.95 nm. Scanning electron microscopy images showed that Cu₃Se₂ nanofilms consisted of uniform, nano-sizes and two-dimensional. It was found through AFM that the surface roughness of the film was 6.173 nm, with a mean particle size of around 50 nm. Depending on the deposition time, the band gaps of the Cu₃Se₂ films were in the range of 2.86–3.20 eV. Three characteristic vibrational modes belonging to Cu₃Se₂ nanofilms were recorded in the Raman spectrum.     

Unexpected Ge–Ge Contacts in the Two‐Dimensional Ge4Se3Te Phase and Analysis of Their Chemical Cause with the Density of Energy (DOE) Function

A hexagonal phase in the ternary Ge–Se–Te system with an approximate composition of GeSe_0.75Te_0.25 has been known since the 1960s but its structure has remained unknown. We have succeeded in growing single crystals by chemical transport as a prerequisite to solve and refine the Ge₄Se₃Te structure. It consists of layers that are held together by van der Waals type weak chalcogenide–chalcogenide interactions but also display unexpected Ge–Ge contacts, as confirmed by electron microscopy analysis. The nature of the electronic structure of Ge₄Se₃Te was characterized by chemical bonding analysis, in particular by the newly introduced density of energy (DOE) function. The Ge–Ge bonding interactions serve to hold electrons that would otherwise go into antibonding Ge–Te contacts.     

Single‐Step Sulfo‐Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu₂ZnSn(S_ySe_1?y)₄ (kesterite) photovoltaic absorbers are synthesized by a one‐step annealing process from copper‐poor and zinc‐rich precursor metallic stacks prepared by direct‐current magnetron sputtering deposition. Depending on the chalcogen source—mixtures of sulfur and selenium powders, or selenium disulfide—as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur‐rich to selenium‐rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as‐grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single‐step sulfo‐selenization method, pentenary kesterite‐based devices with conversion efficiencies up to 4.4 % are obtained.     

Novel Electroless Deposition of Cu<Subscript>3</Subscript>Se<Subscript>2</Subscript> Film on Silicon Substrate by a Simple Galvanic Displacement Process

A novel electroless deposition method for depositing highly uniform adhesive thin films of copper selenide (Cu₃Se₂) on silicon substrates from aqueous solutions is described. The deposition is carried out by two coupled galvanic reactions in a single deposition bath containing copper cations, hydrogen fluoride, and selenous acid: the galvanic deposition of copper on silicon and the subsequent galvanic reaction between the deposited copper with selenous acid in the deposition bath. The powder X-ray diffraction and scanning electron microscopy are used to characterize and examine the deposited films.     

Room temperature formation of Cu3Se2 by solid-state reaction between α-Cu2Se and α-CuSe

Upon being brought into contact with each other, α-Cu₂Se and α-CuSe pellets reacted entirely forming Cu₃Se₂ at room temperature. After 10 days, the reaction was almost completed. Weight measurements revealed that copper atoms migrated from α-Cu₂Se to α-CuSe. Solid-state reactions were also observed in the (α-Cu₂Se+Cu₃Se₂) and (α-Cu₂Se+CuS) systems, but not in the (Cu₃Se₂+α-CuSe), (Cu₂S+CuS) and (α-CuSe+Cu₂S) systems. Therefore, the high ionic conductivity of copper ions in α- and β-Cu₂Se is considered to be responsible for the solid-state reactions observed in these systems.