Study of chemical shift in Ll and Lƞ X‐ray emission lines in different chemical forms of 48Cd and 50Sn compounds using WDXRF technique

Chemical shift in Ll and L? X‐ray emission lines of ₄₈Cd and ₅₀Sn elements in various chemical compounds was determined with high resolution wavelength dispersive X‐ray fluorescence (WDXRF) spectrometer. The positive and negative shifts were measured in ₄₈Cd compounds viz, CdS, CdB₄O₇, CdCl₂, Cd₃(PO₄)₂, CdCO₃, CdI₂ and CdO with reference to pure Cd foil and ₅₀Sn compounds viz, Sn(CrO₄)₂, SnO, SnO₂, SnCl₂, SnF₂, SnF₄ with reference to pure Sn foil. The measured energy shifts in Ll X‐ray emission lines range from ?0.47 to 1.82 eV and L? emission lines range from ?2.67 to 1 eV for both compounds. The effective charges (q, q ^/ , q ^// , and q ^/// ) were calculated from four models (Pauling method, Suchet method, Levine method and Batsonav method) and found to be linear dependence with chemical shift. The measured chemical shifts were correlated with effective charge, number of ligands and electronegativity of the central metal atom in the given compounds.     

Growth and radioluminescence of metal elements doped LiCaAlF6 single crystals for neutron scintillator

The ns²-type metal elements (Pb and Sn) doped LiCaAlF₆ single crystals were grown by a micro-pulling-down (μ-PD) method. Pb doped LiCaAlF₆ [Pb:LiCAF] crystals showed high transparency and single phase of the LiCAF structure. However, we could not obtain Sn:LiCAF crystals due to the evaporation of SnF₂ during the crystal growth. There was an absorption peak around 193 nm in the transmittance spectrum of Pb:LiCAF crystal. In the radioluminescence spectrum of the Pb:LiCAF crystal under X-ray irradiation, two emission peaks around 200 and 830 nm were observed.     

Oxidation of divalent tin in aqueous solutions of SnF2 and 3D transition metals allowed to crystallize slowly in air

Chlorides, nitrates and sulfates of M (M=Mn, Fe, Co, Ni and Zn) were dissolved in aqueous solutions of SnF₂ at M/Sn molar ratios of 0.5 to 3. No HF was used. The solutions were allowed to evaporate in air. Very small amounts of hexagonally shaped crystals of unknown materials were obtained for M=Mn, Co, Ni and Zn. Fe did not yield this phase. X-ray powder diffraction gives identical patterns for the four materials, which are therefore most likely isostructural, and showed that the products are not MSn₂F₆·6H₂O or MSnF₆·6H₂O. Tin-119 Mössbauer spectroscopy gives a single line at negative isomer shift, characteristic of [Sn(IV)F₆]^2– ions.     

Isolated tin fluoride molecules in a copper lattice

A Mössbauer absorber was made by simultaneous evaporation of copper and implantation of¹¹⁹Sn, and postimplantation of F. A large fraction of Sn⁴⁺ was formed, assigned to the formation of SnF₄.     

Molecular dynamics simulation of SnF2 nanostructures in the internal channels of single-walled carbon nanotubes

A molecular dynamics simulation of solid tin(II) fluoride nanostructures formed in internal channels of single-walled carbon nanotubes (SWCNTs) has been performed using two types of model potentials—without and with inclusion of the polarization of ions. For the potential taking into account the polarization of ions, an ordered SnF₂@SWCNT structure is reproduced: in SWCNT(10, 10), it has the form of the SnF₂ internal nanotube. At the same time, the SnF₂@SWCNT(11,11) structure is substantially disordered (glass-like). It has been found that heating of the SnF₂@SWCNT model system produces a superionic state characterized by a high mobility of fluorine ions without migration of tin ions. The model potentials disregard the covalent character of Sn-F bonds and the specific interactions of a lone electron pair of the Sn²⁺ ion. This makes it impossible to completely reproduce the properties of SnF₂ at normal pressures. However, some characteristics of the SnF₂ high-pressure modification can be reproduced if the polarization of ions is taken into account.     

Mössbauer resonance investigations on the SnF2SnF4 system

The Mössbauer resonance spectra of the compounds isolated in the SnF₂SnF₄ system have been studied. The isomer shifts allowed the authors to locate the tin atoms in different chemical environments. The results have been correlated with the electronic structures of both oxidation states of tin and an estimate of the ionicities of the bonding orbitals has been given. For tin(IV) the quadrupole splitting can be explained by means of unequivalent neighboring fluorine atoms. For tin(II) it can be interpreted in terms of p-character and hybrid nature of bonding and non-bonding orbitals. A Goldanskii-Karyagin effect is observed for αSnF₂, Sn₃F₈ and Sn₇F₁₆.     

Bonding in the Doubly Disordered Ba1−x Sn x Cl1+y F1−y Solid Solution

New materials were prepared in the SnF₂/BaCl₂ system by precipitation, and in the SnF₂/BaCl₂/BaF₂ system by direct reactions at high temperature in dry conditions. Stoichiometric BaSn₂Cl₂F₄ and BaSnClF₃?0.8H₂O, and a wide Ba_1?x Sn _x Cl_1+y F_1?y solid solution were prepared for the first time. Elemental analysis, X-ray diffraction and ¹¹⁹Sn Mössbauer spectroscopy were used for the characterization and study of bonding in the new materials. Mössbauer spectroscopy was shown to be an excellent method for probing both the type of bonding at tin(II) (ionic or covalent) and the bond strength at the tin sublattice. Tin(II) is covalently bonded in the stoichiometric phases and ionic (Sn²⁺ stannous ion) in the precipitated Ba_1?x Sn _x Cl_1+y F_1?y solid solution. The case of Ba_1?x Sn _x Cl_1+y F_1?y prepared in dry conditions is more complex. At negative y values (Cl: F <1) and more particularly at high x (solid solution rich in tin), a mixture of Sn²⁺ and covalent Sn(II) is observed, with a normal sublattice strength for Sn(II). At positive y values (Cl:F >1) and more particularly at low x (poor in tin), all the tin(II) is in the ionic form. Furthermore, at high x and high y, the tin(II) sublattice strength decreases so drastically that the tin recoil free fraction at ambient temperature is nearly zero. The bonding type and tin sublattice strength can be explained in terms of preference of covalent bonding with F and when tin clustering occurs, whereas an excess Cl around Sn(II) forms ionic bonding and tin rattling due to ionic size mismatch.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

How amorphous are the tin alloys in li-inserted tin oxides?

Several different metal oxides based anode systems are compared to give insight into their cycling behaviour. The simple electrochemical model for these systems does not usefully predict the ability for a battery to cycle. Pb and Zn oxides cycle less well than Sn oxides, and show more initial crystallinity. SnF₂ and PbF₂ cycle less well than SnO and PbO. Cubic SnP₂O₇ cycles better than the layered polymorph. The nature and structure of the supporting matrix is therefore important in the ability of the tin oxides to cycle. Any material with observable crystallinity in first cycle, will not cycle well. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

The first barium tin(II) bromide fluoride

In an effort to prepare barium tin(II) bromide fluorides for the first time, possibly similar to the chloride fluorides obtained earlier in our laboratory, precipitation reactions were carried out by mixing aqueous solutions of SnF₂ and of BaBr₂.2H₂O. In contrast with the chloride fluoride system, a single powdered phase was obtained throughout the SnF₂ – BaBr₂ system, with the yield being maximum at X ≈ 0.25, where X is the molar fraction of barium bromide in the reaction mixture. Phase identification with the JCPDS database failed to produce a match, confirming that a new phase had been produced. The exact chemical composition of the new compound has not been obtained yet. Based on the X value for the maximum yield, the Sn/Ba ratio is likely to be 3/1 or 2/1. The Mössbauer spectrum at ambient conditions shows that bonding to tin(II) is covalent, therefore with the tin lone pair being stereoactive. The Mössbauer parameters (δ = 3.68 mm/s, Δ = 0.99 mm/s) are similar to those of SnBrF and of Sn₂BrF₅, thereby showing that tin is bonded to both fluorine and bromine. The larger isomer shift and lower quadrupole splitting than in tin(II) fluorides show that the stereoactivity of the tin lone pair is lower than in the fluorides. The Mössbauer parameters fit well the linear correlation of the quadrupole splitting versus the isomer shift” that has been shown to be present in other series of tin(II) compounds. The linear decrease on this correlation shows that the contribution of non-spherical orbitals (p and d) to the lone pair is a much larger contributor to the quadrupole splitting than lattice distortions. The structure is likely made of Ba²⁺ cations and tin(II) fluoride bromide polyatomic anions, with covalent bonding withinthe anions.     

Reaction of stannous fluoride in hydrogen peroxide

The reaction of SnF₂ stannous fluoride with aqueous solutions of H₂O₂ hydrogen peroxide was studied as a function of the molar ratio H₂O₂/SnF₂ in the range 0.02 to 5.00. The products were characterized by thermal analysis, X-ray diffraction and tin119 Mössbauer spectroscopy. The X-ray diffraction pattern of all samples shows only highly broadened lines, characteristic of microcrystalline SnO₂ (average particle diameter: 39 Å). Thermal analyses show that the material is hydrated. Mössbauer spectroscopy gives a broad single line at approximately 0 mm/s, characteristic of SnO₂ for all samples, and in some cases a tin(II) doublet with =3.1 mm/s and =1.9 mm/s.     

Mössbauer lattice parameters of the various compounds in the SnF2−SnF4 system

Four distinct compounds have been reported in the SnF₂?SnF₄ system: Sn₇F₁₆, Sn₃F₈, Sn₂F₆ and Sn₁₀F₃₄. A Mössbauer study has been carried out on these fluorides over the temperature range 4.2≤T≤473 K in order to determine the recoilless fractionf for the two tin nuclei.     

Oxidation of SnF2 stannous fluoride in aqueous solutions

The rate of oxidation of SnF₂ in aqueous solutions has been studied by redox titrations and Mössbauer spectroscopy on frozen solutions versus the acidity of the solutions and versus time. Tin(II) oxidizes in aqueous solutions; however, the rate of oxidation is much slower than previously reported. Redox titrations show that the amount of tetravalent tin increases continuously with time. Oxygen dissolved in water seems to be the oxidizing species. The oxidation rate is faster in acidic solutions. Mössbauer spectroscopy on frozen solutions shows the slow formation of tetravalent tin; it also indicates that divalent tin in aqueous solutions is similar to that observed in solid SnF₂, except that one water molecule coordinates tin.     

EPR of Mn2+ in single crystals of [Zn(H2O)6]SnF6 and [Co(H2O)6]SnF6; Co2+ spin-lattice relaxation time

EPR studies have been carried out in Mn²⁺-doped single crystals of [M(H₂O)₆]SnF₆ (M  Zn, Co) at different temperatures using X-band microwave frequency. Mn²⁺ has been found to substitute for Zn²⁺ or Co²⁺ exhibiting a unique magnetic complex with z-axis directed long the c-axis of the crystals. Observation of resolved Mn²⁺ spectrum in [Co(H₂O)₆]SnF₆ and broadening of the resonance lines on cooling the crystals have been explained on the basis of host spin-lattice relaxation narrowing. The T₁ of Co²⁺ has been estimated to be ≈ 1.8 × 10⁻¹² s at 293 K.     

Formation of gold nanoparticles in gold ruby glass: The influence of tin

A ¹¹⁹Sn Mössbauer study was carried out of tin(IV) complexes with 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) and its N(4)-methyl (H2Bz4M) and N(4)-phenyl (H2Bz4Ph) derivatives: [Sn(2Bz4DH)Cl₃] (1), [Sn(2Bz4DH)PhCl₂] (2), [Sn(2Bz4M)Cl₃] (3), [H₂2Bz4M]₂[Ph₂SnCl₄] (4), [Sn(2Bz4Ph)PhCl₂] (5), [Sn(2Bz4Ph)Ph₂Cl] (6), in which H2Bz4R stands for the neutral ligand and 2Bz4R stands for the anionic thiosemicarbazone. In addition, ¹¹⁹Sn Mössbauer studies of the tin(IV) complexes [Sn(H4Bz4DH)₂Cl₄H₂O] (7), [Sn(H4BzPS)₂Cl₄H₂O] (8) with 4-benzoylpyridine thiosemicarbazone (H4Bz4DH) and the correspondent semicarbazone (H4BzPS) were performed. The isomer shifts decrease upon coordination due to the variation in the percentage of s character as tin changes from approximately sp³ hybridization in the tin salts to sp³d² in the octahedral or sp³d³ in the heptahedral complexes. The Mössbauer parameters of compound (4) showed the existence of two tin(IV) sites, which have been attributed to the presence of the cis and trans isomers.     

Mössbauer studies of heteroleptic Sn(II) derivatives

The heteroleptic Sn(II) derivatives, [Sn(η⁵-C₅Me₅)Cl] (1), [{Sn(η⁵‐C₅Me₄SiMe₂Bu^t)} {Sn(η⁵‐C₅Me₄SiMe₂Bu^t)(OSO₂CF₃)}] (2), [{Sn(η⁵‐C₅Me₅)}{Sn(η⁵‐C₅Me₅)(OSO₂CF₃)}] (3) and [(Sn{N(SiMe₃)₂}{OSO₂CF₃})₂] (4), were prepared and characterized by ¹¹⁹Sn Mössbauer spectroscopy, as well as by other techniques such as multinuclear NMR (solution‐ and solid‐state) spectroscopy and X‐ray crystallography. The ¹¹⁹Sn Mössbauer spectroscopic data were in good agreement with the other solid state results rendering additional support for the elucidation of bonding and structural features of these compounds.     

Control Al/Mg intermetallic compound formation during ultrasonic-assisted soldering Mg to Al

To prevent the formation of Al/Mg intermetallic compounds (IMCs) of Al₃Mg₂ and Al₁₂Mg₁₇, dissimilar Al/Mg were ultrasonic-assisted soldered using Sn-based filler metals. A new IMC of Mg₂Sn formed in the soldered joints during this process and it was prone to crack at large thickness. The thickness of Mg₂Sn was reduced to 22 μm at 285 °C when using Sn-3Cu as the filler metal. Cracks were still observed inside the blocky Mg₂Sn. The thickness of Mg₂Sn was significantly reduced when using Sn-9Zn as the filler metal. A 17 μm Mg₂Sn layer without crack was obtained at a temperature of 200 °C, ultrasonic power of Mode I, and ultrasonic time of 2 s. The shear strengths of the joints using Sn-9Zn was much higher than those using Sn-3Cu because of the thinner Mg₂Sn layer in the former joints. Sn whiskers were prevented by using Sn-9Zn. A cavitation model during ultrasonic assisted soldering was proposed.     

Cu(In,Sn)Se2 thin films for absorption of energy from infrared radiation

In this study, we sought to lower the bandgap of thin film solar cells by replacing the Ga used in the absorber layer of Cu(In,Ga)Se₂ with Sn (bandgap of 0.07?eV) to form Cu(In,Sn)Se₂. The proposed scheme was shown to reduce the bandgap of the absorber layer from 1.0?eV to 0.88?eV. Sn films of various thicknesses were deposited using precursors of Sn–In–Cu metal in order to study the effects of Sn/(In?+?Sn) ratio (SIR) on the structure of the material and photoelectrical characteristics of the Cu(In,Sn)Se₂ absorber layer. Experiment results revealed that a higher SIR following selenization increased the grain size and surface roughness of the absorber layer. It increased the quantity of secondary phases of SnSe₂ and Cu₂SnSe₃ and improved the distribution of Cu and In in the absorber layer. A higher SIR was also shown to increase electron mobility while decreasing carrier concentration and conductivity. When SIR≧0.25, the replacement of In³⁺ with Sn⁴⁺in the Cu⁺ vacancies decreased the electron strength of In. We speculate that an increase in SIR caused a relative increase in the quantity of Sn²⁺ compared to Sn⁴⁺, thereby increasing the electron strength of Sn and switching the absorber layer from a p-type to an n-type semiconductor.     

Crystal structure and Mössbauer spectroscopic study of FeSnF6·6H2O

Large single crystals of FeSnF₆·6H₂O were grown when aqueous hydrofluoric solutions of SnF₂ and FeF₂ were allowed to evaporate in air. Tin-119 Mössbauer spectroscopy at ambient temperature shows a single line at slightly negative isomer shift relative to CaSnO₃ at room temperature (=–0.380(6) mm/s, =0). This is characteristic of tetravalent tin octahedrally coordinated by fluorine. The X-ray crystal structure shows that tin(IV) is coordinated by 6 fluorine atoms, and Fe(II) by 6 water molecules. Both sites show a slight distortion from octahedral symmetry: the six distances are equal (Sn-Fe=1.941(3) Å and Fe-O=2.112(3) Å), whereas there are two values of angles (Fe-Sn-F=90.4(1)° and 89.6(1)°; O-Fe-O=91.1(1)° and 88.9(1)°). The material is an ionic compound [SnF₆]^2–[Fe(H₂O)₆]²⁺.     

Specific features of Bi2Te3 doping with Sn

The effect of doping bismuth telluride with tin, on its electrophysical properties, has been studied. It is shown that the main features in the transport coefficients of Bi₂Te₃:Sn can be explained by the existence of resonant Sn states within the valence band. The existence of resonant Sn states was confirmed by codoping Bi₂Te₃:Sn with the electroactive impurity I. Fiz. Tverd. Tela (St. Petersburg) 40, 1428–1432 (August 1998)