Formation and properties of copper chalcogenides thin films on polymers formed using sodium telluropentathionate

The preparative conditions were optimized to get chalcogens layers on the polymer — polyamide PA surface by sorption at room temperature using sodium telluropentathionate, Na₂TeS₄O₆. Further interaction of chalcogenized dielectric with copper’s (I/II) salt solution leads to the formation of mixed Cu_xS_y-Cu_xTe_y layers. Optical, electrical and surface characteristics of the layers are highly controlled by the deposition parameters. The stoichiometry of these layers was established by UV-Visible and AA spectrometry. Optical absorption (transmittance) experiments show the samples are of high optical quality. The band gaps of thin films were obtained from their optical absorption spectra, which were found in the range of 1.44–2.97 eV. XRD was used in combination with AFM to characterize chalcogenides layers’ structural features. XRD analysis confirmed the formation of mixed copper chalcogenides’ layers in the surface of PA with binary phases such as Cu₂Te, Cu_3.18Te₂, copper telluride, Cu_2.72Te₂, vulcanite, CuTe, anilite, Cu₇S₄ and copper sulfide, Cu_1.8S. The crystallite sizes of thin films calculated by the Scherer formula were found to be in the range of 3.07–13.53 nm for Cu_xS_y crystallites and 4.06–20.79 nm for Cu_xTe_y crystallites. At room temperature an electrical resistance of Cu_xS_y-Cu_xTe_y layers varies from 3.0×10³ kΩ□^?1 to 1.0 kΩ□^?1.      

Das Massenspektrum des Systems Te/S und der chemische Transport von Tellur mit Schwefel

Mass Spectrum of the System Te/S and the Chemical Transport of Tellurium with Sulphur The mixed molecules TeS_x (x = 1 … 7) and Te₂S_y (y = 1 … 6) have been observed by mass spectrometry. These molecules are responsible for the fact, that Tellurium can be chemically transported by means of sulphur in a temperature gradient (375 → 325°C).     

Comparison of the efficacy of sulfurization agents in decreasing the sheet resistance of polyamide and polyethylene with copper sulfide layers and influence of their compositions

The process of obtaining semiconductive and electrical conductive layers of copper sulfides by the sorption — diffusion method on polymers (polyamide 6 and low density polyethylene) using solutions of potassium pentathionate, K₂S₅O₆, and higher polythionic acids, H₂S _n O₆ (n = 21, 33), was investigated. The layers were characterized for compositional and electrical properties by X-ray diffraction (XRD) analysis and sheet resistance measurements. The thickness of copper sulfides layers on polyamide and polyethylene increased with increasing time of polymer sulfurization and varied from 10 to 43 μm. The variations of the sheet resistance of copper sulfides layers formed on the surface of polymers on sulfurization agent used, the conditions of sulfurization, chemical and phase composition of the obtained layers were established. Sheet resistance of copper sulfides layers decreases with increasing time of the duration of sulfurization and the number of sulfur atoms in the polythionate anion. The sheet resistance values for copper sulfide layers formed on the polyamide surface are much lower than those of Cu _x S formed on the polyethylene surface. XRD showed the predomination of Cu _x S phases with low x values.      

The structural, magnetic, hydrogenation and electrode properties of REMg2Cu9?xNix alloys (RE=La, Pr,Tb)

The LaMg₂Cu₉, PrMg₂Cu₉, LaMg₂Cu₄Ni₅, PrMg₂Cu₄Ni₅ and TbMg₂Cu₆Ni₃ alloys were prepared for the investigations of crystal structure, magnetic and hydrogen storage properties. The magnetic properties of several REMg₂Cu_9−xNi_x compounds have been studied up to 9 T and from 2 to 300 K. Tb compounds show a ferrimagnetic (with Ni) or antiferromagnetic (without Ni) behaviour, which can be attributed to the Tb magnetic structure. At high temperature a paramagnetic Curie Weiss behaviour is observed and the effective moment corresponds to that of Tb. A magnetic contribution of Pr moment is observed in both Pr compounds, with larger magnetization for PrMg₂Cu₄Ni₅ and a transition at 3 K. The hydrogen absorption occurs at 95 bar for LaMg₂Cu₉ (3 H f.u.⁻¹) and above 2 bars for LaMg₂Cu₄Ni₅ (1.6 H f.u.⁻¹). The effect of Cu-Ni substitution on the electrochemical properties of LaMg₂M₉ ternary alloys was investigated leading to maximum discharge capacity of 250–310 mAh g⁻¹.      

Comparison characterization of copper selenide thin layers prepared on polyamide 6 films by sorption-diffusion method

Some earlier synthesized copper selenide (Cu _x Se) layers formed on the surface of polyamide 6 by sorption-diffusion method using potassium selenotrithionate (K₂SeS₂O₆) as precursor of selenium were characterized by the XRD, XPS and SEM methods. According to the results of the SEM studies, the most uniform Cu _x Se layers form at the 2.5 h polyamide seleniumized duration at the temperature of 60°C. The thickness of layers, which dependeds on the duration of seleniumization, changed in the range of 0.8–3.2 µm. The XRD patterns of not previously studied Cu _x Se layers showed their phase composition of six copper selenides: Cu₂Se, two phases of CuSe₂, Cu₃Se₂, berzellianite, Cu_2-x Se, and bellidoite Cu₂Se. Analysis of the XRD and XPS data shows that the macrostructure and composition of the Cu_xSe layers depend on the conditions of formation of these layers.      

Thermodynamic study of Cu-Tl-Te system using EMF technique with Cu<Subscript>4</Subscript>RbCl<Subscript>3</Subscript>I<Subscript>2</Subscript> solid electrolyte

The EMF method with a solid Cu⁺-conducting electrolyte of Cu₄RbCl₃I₂ was sued to study the Cu-Tl-Te system in the temperature range of 300–420 K. A diagram of solid-phase equilibriums of this system is constructed, partial molar functions of copper in alloys, standard thermodynamic functions of formation and standard entropies of CuTlTe₂, CuTl₄Te₃, Cu₂TlTe₂, Cu₃TlTe₂, Cu₉TlTe₅ triple compounds and Cu _x Tl_{5 − x} Te₃ solid solutions (0 < x < 1) are calculated. The obtained results confirmed the assumption as to the possibility of using this modification for the EMF technique for thermodynamic studies of copper-containing triple systems, even if they contain a less noble component than copper.     

Reactions of M3Te7 (M = Mo, W) clusters with electrophilic reagents: Chalcogen exchange in the Te2 ligand and the first complexes of (TeS)

Reactions of triangular telluride-bridged Mo and W clusters [M₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺ (M = Mo, W; dtp = (EtO)₂PS₂) with S₂Cl₂ or Br₂ lead to Te/S exchange in the Te₂ ligands, with the formation of complexes with a novel TeS²⁻ ligand. Reaction of [W₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺ with Br₂ or S₂Cl₂ gives a mixture of complexes formulated as [W₃Te_4.25S_2.75(dtp)₃]⁺ and [W₃Te_4.30S_2.70(dtp)₃]⁺, respectively, on the basis of X-ray structural analysis. Reaction of the Mo homolog, namely [Mo₃(μ₃-Te)(μ₂-Te₂)₃(dtp)₃]⁺, with S₂Cl₂ gives rise to [Мо₃Te_4.74S_2.26((EtO)₂PS₂)₃]⁺. Electrospray ionization mass spectrometry (ESI-MS) complements the information gathered from X-ray analysis regarding the degree of Te by S substitution; moreover, detailed insights on the regioselectivity of such replacement are also obtained from ESI-MS analysis. These experimental evidences indicate that Te by S replacement in W complexes display high regioselectivity (as evidenced by the exclusive formation of a W₃Te₄S₃⁴⁺ core), the equatorial Te ligands being preferentially replaced over the Te_ax and μ₃-Te ligands. Conversely, for the Mo homologs, a broad distribution of Mo₃Te_7−xS_x⁴⁺ cluster species ranging from x = 0 to 6 is observed. Bond distance analysis as well as crystal packing trends as a function of the cluster core M₃Te_7−xS_x⁴⁺ (M = Mo, W; x = 0–6) composition are also reported.     

Untersuchungen über die Kinetik der Wechselwirkung zwischen Cu2S und TeO2

The kinetics of the interaction of Cu₂S and TeO₂ for mixtures, of molar ratio Cu₂S/TeO₂: 1/1, 1/1.5, and 1/2, was investigated in the temperature range between 500 and 900°C. The interaction takes place with high rate. The over-all interaction products up to temperatures 500–600°C, contain predominantly copper tellurites and elementary tellurium. At higher temperatures Cu_2–x Te, Cu_4–x Te₂, CuTe or their mixtures are obtained, in dependance of the quantity of TeO₂ in the starting batches.     

Etude structurale des sulfotellurures de terres rares (LS)2Te1+x (L = Tb,Dy, Ho,Er, Tm et Y). I. Sous-structure de la phase ordonnée de (HoS)2Te1,34. Structure de la phase desordonnée de (TbS)2Te

The lanthanide sulfotellurides (LS)₂Te_1+x (0 ≤ x < 0.50) show order-disorder phenomena. Above 450°C, they crystallize in a partially disordered structure, orthorhombic with cell parameters a, b, and c close to 4.1, 5.2, and 13.6 Å, respectively. This structure is determined from diffractometer data on a (HoS)₂Te_1.34 crystal (R = 0.061). It is built up along the c axis from (L₄S) tetrahedra layers, separated by Te planes. Disorder and nonstoichiometry are related to the two vacant Te sites.     

Ceramic materials made of CdTe and Cd-Zn-Te nanocrystalline powders

In the present study newly produced semiconductor ceramic nanopowder materials made of CdTe and Cd_1−xZn_xTe (CZT) are considered. Common features and differences in microstructures, phase transformations, grain growth and properties of the ceramic materials of the binary and ternary compositions are studied.      

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.     

The effect of calcium substitution on the afterglow of Eu2+/Dy3+ doped Sr4Al14O25

The effect of calcium substitution on the afterglow of tetrastrontium aluminate phosphors (Sr₄Al₁₄O₂₅:Eu²⁺, Dy³⁺) was investigated. A series of (Sr₁-_xCa_x)O⊎nAl₂O₃:Eu²⁺(1%), Dy³⁺(0.5%), with variation of calcium content (x = 0 − 1), were synthesized by a high temperature solid state reaction in a reducing atmosphere. The photoluminescence, persistent luminescence (afterglow), and lumen equivalents of these materials were studied and compared. It turned out that the afterglow properties of the phosphors were strongly dependent on the Sr/Ca ratio. As the Ca content increased, a phase transition and blue shift in emission spectra were observed.      

Two new layered oxohalides in the system Cu–Yb–Te–O–Cl

Two complex lanthanide(III) transition metal(II) tellurium(IV) oxyhalides, Cu₃Yb₂(TeO₃)₄Cl₄ and Cu₃Yb₃(TeO₃)₄Cl₆ have been synthesized and the crystal structures were determined by single-crystal X-ray diffraction. Both compounds are layered with only weak connections in between the layers. The layers are made up of [YbO₈], [TeO₃] and [CuO_xCl_y] polyhedra. In both compounds the strong Lewis acid cations Yb³⁺ and Te⁴⁺ only form bonds to oxygen while Cu²⁺ form bonds to both oxygen and chlorine. This leads the Cl^? ions to be expelled from the bonding volumes of the crystal structures and protrude from the layers. Magnetic susceptibility measurements were performed on a powder sample of Cu₃Yb₂(TeO₃)₄Cl₄. The Curie–Weiss law found at low temperatures indicates a Curie–Weiss temperature of ca. ?5(1) K. However, indication for long-range magnetic ordering could not be observed down to 1.87 K. The two new phases are to the best of our knowledge the first containing all three of Cu, Yb and Te.     

Formation and characterization of Cu<Subscript>x</Subscript>S layers on polyethylene film using the solutions of sulfur in carbon disulfide

Results of the formation of copper sulfide layers using the solutions of elemental sulfur in carbon disulfide as precursor for sulfurization are presented. Low density polyethylene film can be effectively sulfurized in the solutions of rhombic (α) sulfur in carbon disulfide. The concentration of sulfur in polyethylene increases with the increase of the temperature and concentration of sulfur solution in carbon disulfide and it little depends on the duration of sulfurization. Electrically conductive copper sulfide layers on polyethylene film were formed when sulfurized polyethylene was treated with the solution of copper (II/I) salts. Cu_xS layer with the lowest sheet resistance (11.2 Ω cm⁻²) was formed when sulfurized polyethylene was treated with copper salts solution at 80°C. All samples with formed Cu_xS layers were characterized by X-ray photoelectron spectroscopy. XPS analysis of obtained layers showed that on the layer’s surface and in the etched surface various compounds of copper, sulfur and oxygen are present: Cu₂S, CuS, CuO, S₈, CuSO₄, Cu(OH)₂ and water. The biggest amounts of CuSO₄ and Cu(OH)₂ are present on the layer’s surface. Significantly more copper sulfides are found in the etched layers.     

Synthesis, crystal and electronic structure, and physical properties of the new lanthanum copper telluride La3Cu5Te7

The new lanthanum copper telluride La₃Cu_5−xTe₇ has been obtained by annealing the elements at 1073 K. Single-crystal X-ray diffraction studies revealed that the title compound crystallizes in a new structure type, space group Pnma (no. 62) with lattice dimensions of a=8.2326(3) Å, b=25.9466(9) Å, c=7.3402(3) Å, V=1567.9(1) Å³, Z=4 for La₃Cu_4.86(4)Te₇. The structure of La₃Cu_5−xTe₇ is remarkably complex. The Cu and Te atoms build up a three-dimensional covalent network. The coordination polyhedra include trigonal LaTe₆ prisms, capped trigonal LaTe₇ prisms, CuTe₄ tetrahedra, and CuTe₃ pyramids. All Cu sites exhibit deficiencies of various extents. Electrical property measurements on a sintered pellet of La₃Cu_4.86Te₇ indicate that it is a p-type semiconductor in accordance with the electronic structure calculations.     

Dependence of the magnetic properties of MnGaN epitaxial layers on external electrical field

Investigation of the magnetic properties of MnGaN epitaxial layers as a function of external electrical field was performed on the basis of field effect structure. The structure included substrate of n-type GaN, epitaxial layer of n-type Mn_xGa_1-xN, dielectric layer and metal layer acting as field effect device gate. Each Mn atom in Mn_xGa_1-xN contributes 4 net spins due to the electrons occupying energy levels ⁴F, ⁴D, ⁴P and ⁴G belonging to 3d orbital, and these levels are in the energy band gap and in the top of the valence band of Mn_xGa_1-xN. The position of the Fermi level is determined to be in the energy band gap of the layer of GaN and to be above the level 4F in the layer of Mn_xGa_1-xN. In this way application of external negative voltage on the gate causes change in the number of electrons contributing net spins and the saturation magnetization M_sat of Mn_xGa_1-xN changes as well. It was found that M_sat changes in the range 1.15 × 10⁻³–0.7 × 10⁻³ A μm⁻¹ if the external voltage changes in the interval 0–−5V. The application of this structure for the design of spintronic devices is discussed in this paper.      

Investigation of Zn<Subscript>m</Subscript>Cd<Subscript>n</Subscript>X<Subscript>y</Subscript> (y = m + n; X = Te,Se and S) Clusters with TDDFT Method

Based on zinc blende and wurtzite structures of experimental ZnTe and CdTe nanocrystals, Zn_mCd_nX_y (X = Te, Se and S) clusters were investigated using DFT/B3LYP/LANL2DZ. From analyses of their characters of conformations, HOMO–LUMO gaps, Raman and absorption spectra, Mulliken charges and WBI (Wiberg Bond Index) values, we have discovered that Zn_mCd_nTe_y, Zn_mCd_nSe_y and Zn_mCd_nS_y molecules had similar characters. In this paper, characters of Zn_mCd_nTe_y were investigated in detail. First, we have found that HOMO–LUMO gaps, Raman spectra, absorption spectra, bond lengths and Mulliken charges of doping Zn₂CdTe₃, ZnCd₂Te₃, Zn₃CdTe₄, Zn₂Cd₂Te₄ and ZnCd₃Te₄ structures were in the scope of corresponding naked ZnTe and CdTe clusters. These characters of doping Zn_mCd_nTe_y molecules show that their stabilities are good. Second, comparing with ZnTe structures, the wavelengths of the absorption peaks of doping Zn_mCd_nTe_y clusters shift to red in water environment. Moreover, with increasing of the number of Cd atom, their wavelengths of the absorption peaks gradually shift to red. This conclusion is consistent with the experimental fact. Third, Raman spectra of pure ZnTe clusters have higher frequencies than corresponding naked CdTe structures. As for doping molecules, the frequencies of their Raman spectra gradually shift to low frequencies with increasing of Cd atoms’ number.     

Electrochemical study of spinel oxide systems with nominal compositions Ni1− x Cu x Co2O4 and NiCo2− y Cu y O4

Studies on the electrochemical behaviour of Ni_{1− x} Cu _x Co₂O₄ (x ≤ 0.75) and NiCo_{2− y} Cu _y O₄ (y ≤ 0.30) electrodes in 5 mol dm⁻³ KOH aqueous solutions are presented. The oxide layers have been prepared by thermal decomposition of aqueous nitrate solutions on nickel supports at 623 K. Powder samples were also prepared by thermal decomposition under the same conditions. The powder samples and the oxide layers were characterised by X-ray powder diffraction. The influence of the copper content on the voltammetric response of the electrodes and activity towards oxygen evolution reaction is analysed and correlated with the surface composition of the electrodes by means of X-ray photoelectron spectroscopy data. The analysis of the results reveals that the presence of Cu affects the electrode behaviour and its influence depends on which cation has been replaced. Received: 22 February 1999 / Accepted: 26 October 1999     

Darstellung und Struktur von K3(SH)TeS3

Preparation and Crystal Structure of K₃(SH)TeS₃ K₃(SH)TeS₃ has been prepared and structurally characterized. It crystallizes cubic with a = 1270(2) pm, space group 143m. The SH- Ions are surrounded by an octahedron of K⁺ ions. The TeS₃^2?. anions form flat trigonal pyramids with Te? S distances of 234.8(2) pm.