Transformation of the electronic structure of the SnO2 − x /MWCNT nanocomposite under high-vacuum annealing conditions

The transformation of the structural phase state and the electronic structure of the SnO_{2 ? x} /MWCNT composite has been studied using X-ray spectroscopy and high-resolution transmission electron microscopy. It has been shown that the character of the interaction of the metal-oxide component of the composite with the array of carbon nanotubes depends on the structural state of tin oxide in globules of the metal-oxide component. In the initial composite with a large content of amorphous tin oxide, covalent functionalization of the MWCNT surface occurs. High-vacuum annealing results in the formation of a nanocrystalline structure in globules of the metal-oxide component and is accompanied by changes in the character of its interaction with carbon tubes.     

Controlled SnO2 nanocrystal growth in SiO2–SnO2 glass‐ceramic monoliths

Crack‐free (100–x) SiO₂–x SnO₂ glass‐ceramic monoliths have been prepared by the sol–gel method obtaining for the first time SnO₂ concentrations of 20% with annealing at 1100 °C. Heat‐treatment resulted in the formation and growth of SnO₂ nanocrystals within the silica matrices. Combined use of Fourier transform–Raman spectroscopy and in situ high‐temperature X‐Ray diffraction shows that SnO₂ particles begin to crystallize in the cassiterite‐type phase at 80 °C and that their average apparent size remains around 7 nm, even after annealing at 1100 °C. Nanocrystal sizes and size distributions determined by low‐wavenumber Raman are in good agreement with those obtained from transmission electron microscopy measurements. Results indicate that the formation and the growth of SnO₂ nanocrystals impose a residual porosity in the silica matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Study of Au/SnO x –Al2O3 catalysts used in CO oxidation by in situ Mössbauer spectroscopy

The active catalytic components in tin oxide containing alumina-supported gold catalyst were examined by comparing and analysing the in situ Mössbauer spectra of the SnO _x –Al₂O₃ support and the 3 wt.% Au/SnO _x –Al₂O₃ catalyst (1.1 wt.% Sn, Au/Sn = 3:2 atomic ratio). Samples were prepared by using organometallic precursor of ¹¹⁹SnMe₄ (enriched). First tin was grafted to the alumina surface from the organometallic precursor compound. In the next step the grafted complexes were decomposed in flowing oxygen. Gold was deposited onto the SnO _x –Al₂O₃ support in the subsequent step. Analysis of in situ spectra shows that in Au/SnO _x –Al₂O₃ catalyst after activation in hydrogen at 620 K tin may occur in three different oxidation states [Sn (IV), Sn(II) and Sn(0)] simultaneously. The metallic tin is a component of the bimetallic AuSn alloy phase. Data presented provide the first evidence for the formation of alloy-type supported Sn–Au catalyst on alumina. Furthermore, from the spectra recorded at different temperatures, values of the Debye temperatures and recoilless fractions were also determined for the various species. The results show that in catalytic oxidation of carbon monoxide at room temperature the dominant part of Sn(II) and the AuSn alloy is oxidized.     

Formation mechanisms of nanocomposite layers based on multiwalled carbon nanotubes and non-stoichiometric tin oxide

Nanocomposite layers based on multiwalled carbon nanotubes (MWCNTs) and non-stoichiometric tin oxide (SnO _x ) have been grown by magnetron deposition and CVD methods. In the case of the CVD method, the study of the structure and phase composition of obtained nanocomposite layers has shown that a tin oxide “superlattice” is formed in the MWCNT layer volume, fixed by SnO _x islands on the MWCNT surface. During magnetron deposition, the MWCNT surface is uniformly coated with tin oxide islands, which causes a change in properties of individual nanotubes. Electrical measurements have revealed the sensitivity of nanocomposite layers to (NO₂)⁻ molecule adsorption, which is qualitatively explained by a change in the conductivity of the semiconductor fraction of p-type MWCNTs.     

Low-temperature photoluminescence of ion-implanted SiO2:Sn+ films and glasses

Low-temperature photoluminescence spectroscopy with pulsed synchrotron excitation is applied to study the regularities of excitation and relaxation of both point defects and nanoparticles formed by tin implantation into SiO₂ films and glasses. It has been found that tin implantation followed by air and nitrogen annealing yields the formation of α-Sn nanoclusters and nonstoichiometric SnO _x nanoparticles, while a stable phase of SnO₂ does not appear. Alternative channels of luminescence excitation are revealed for nanoclusters, including energy transfer from excitons and electron-hole pairs of the host SiO₂ matrix.     

Phase transformation and magnetic properties of SmCo7−xBx alloys prepared by mechanical alloying

The phase transformation and magnetic properties of SmCo_7−xB_x (x=0, 0.2, 0.5 and 1) alloys prepared by mechanical alloying have been investigated systematically. The coercivities of the alloys without B increase with increasing annealing temperature, as a consequence of complete crystallization of TbCu₇-type phase. The substitution of B for Co is favorable to the formation of Th₂Zn₁₇- and CaCu₅-type phases when annealed at 650°C, accompanied by the enhancement of the coercivities. Increasing the annealing temperature causes the formation of soft magnetic phase Sm₂Co₁₄B in the B-substituted alloys. In the alloys with x=0.5 and 1 annealed at 850°C, the major phase is Sm₂Co₁₄B, which degrades the magnetic properties sharply. A remanence enhancement has been observed in the SmCo_7−xB_x alloys due to the exchange coupling of the nanoscale structure.     

Interfacial interaction in a composite based on multi-walled carbon nanotubes and amorphous tin oxide

The specific features of changes in the electronic structure of multi-walled carbon nanotubes (MWCNTs) due to the interaction with an amorphous tin oxide in the SnO_x/MWCNT composite formed by magnetron sputtering have been investigated using X-ray spectroscopy. It has been shown that the formation of chemical bonds responsible for significant changes in the local and electronic structures of the outer layers of MWCNTs occurs at the boundaries of the “amorphous oxide/MWCNT” contacts. The vacuum annealing of the composite leads to the disturbance of the chemical interaction at interfaces of the composite and to a partial recovery of the local structure of the outer layers of MWCNTs. A decrease in the amount of oxygen in the tin oxide under vacuum annealing conditions causes an increase in the number of unpaired Sn 5s electrons, which, in turn, enhances the charge transfer through the interfaces in the composite and leads to a splitting of the π^*-subsystem of the outer layers of MWCNTs.     

Mössbauer study of SnO<Subscript>2</Subscript> powders doped with dilute <Superscript>57</Superscript>Fe prepared by a sol-gel method

SnO₂ powders, doped with various ⁵⁷Fe contents were prepared by a sol-gel method, and annealed finally at 500 °C and 650 °C. These samples were characterized by Mössbauer spectroscopy, vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) to investigate the relationship of magnetic properties, grain sizes, annealing temperatures and Mössbauer parameters. The particle sizes of SnO₂ powders reduced to less than 100 nm with the increase of Fe contents up to 5%. Rutile SnO₂ was the only phase obtained for all samples. Room temperature Mössbauer spectra suggest the presence of two different paramagnetic iron sites for all samples and one magnetically relaxed species for those samples with the lowest iron concentrations. The magnetization increased with the Fe content, but was reduced for the samples annealed at 650 °C perhaps due to a segregation of α-Fe₂O₃ doped with tin.     

Heat treatment effects on spinel phase of Zn x Ni1 − x Fe2O4 and MnFe2O4 nanoferrites

We report the effects of heat treatment on Zn _x Ni_1???x Fe₂O₄ (x?= 0, 0.5 and 1.0) and MnFe₂O₄ ferrite nanoparticles. The as-prepared compounds were sintered from 400°C to 1100°C. Pure ZnFe₂O₄ (x?= 1.0) and MnFe₂O₄ could be obtained under low reaction temperature of 200°C. NiFe₂O₄ (x?= 0) and Zn_0.5Ni_0.5Fe₂O₄ (x?= 0.5) nanoferrites crystallized with single phase cubic spinel structure after annealing at 600°C. The single phase cubic spinel structure of these compounds was destroyed after annealing at temperature above 700°C. The magnetization measurements indicate superparamagnetic behavior of the nanosized compounds produced.     

Phase transformations in the Mn-Ge system and in Ge x Mn1 ? x diluted semiconductors

Results of an X-ray diffraction study as well as magnetic and electrical measurements of the solid-state reactions in Ge/Mn polycrystalline films of an 80/20 atomic composition have been presented. It has been shown that the ferromagnetic Mn₅Ge₃ phase is formed first on the Ge/Mn interface after annealing at ??120°C. The further increase in the annealing temperature to 300°C leads to the beginning of the synthesis of the Mn₁₁Ge₈ phase, which becomes dominating at 400°C. The existence of new structural transitions in the Mn-Ge system in the region of ??120 and ??300°C has been predicted on the basis of the presented results and results obtained earlier when studying solid-state reactions in different film structures. The supposition about the general chemical mechanisms of the synthesis of the Mn₅Ge₃ and Mn₁₁Ge₈ phases during the solid-state reactions in the Ge/Mn films of the 80/20 atomic composition and the phase separation in Ge _x Mn_{1 ? x} (x > 0.95) diluted semiconductors has been substantiated.     

Studies of oxidation of iron nanowires encased in porous aluminium oxide template

The transformations of phase composition of iron nanowires deposited into porous alumina template when annealing in the air were studied. The samples of iron nanowires of different diameter (8, 13, 15, 30 nm) were annealed for 1.5 h at temperature up to 600°C. In addition, for nanowires of 15 nm diameter the dependence of phase composition on annealing time was investigated. The phases were determined by applying Mössbauer spectroscopy. New Fe(II) and Fe(III) contributions to Mössbauer spectra were found and those were indentified as caused by the formation of hercynite FeAl₂O₄ and (Fe _x Al_1???x )₂O₃ with small x values (x?≤?0.15). It has been found that though initially the Fe(II) compound forms rapidly, afterwards its formation rate becomes lower than that of Fe(III) and after longer annealing time the Fe(III) content exceeds Fe(II) one.     

Size-dependent luminescence of Sm3+ doped SnO2 nano-particles dispersed in sol-gel silica glass

Sol-gel glasses with composition (100?x)SiO₂–xSnO₂ doped with 0.4 mol% of Sm³⁺, with x ranging from 1 to 10, have been successfully synthesized. Transparent doped nano-glass-ceramics were prepared by thermal treatment of the precursor glasses at 900°C during 4 hours, leading to nanocomposites comprising SnO₂ nanocrystals embedded into an amorphous SiO₂ phase. A structural analysis in terms of X-ray Diffraction and High Resolution Transmission Electron Microscopy confirms the precipitation of SnO₂ nanocrystals within the glassy matrix. The mean radius of the obtained SnO₂ nanocrystals, ranging from 2.1 to 4.7 nm calculated by the Scherrer and Brus equations, similar to the Bohr’s exciton radius, constitutes a wide band-gap semiconductor quantum-dot system. Energy transfer from SnO₂ nanocrystal host to Sm³⁺ ions is confirmed by luminescence spectra and analyzed as a function of SnO₂ concentration, showing an evolution that could be ascribed to selective excitation of nanocrystal sets with predetermined size. Besides, a study of the luminescence as a function of temperature helps to clarify the involved energy transfer mechanisms.     

AES and XPS studies of a por-Si/SnOx nanocomposite formed using a powerful ion beam of nanosecond duration

The results of the X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and scanning electron microscopy (SEM) investigations of tin-oxide nanolayers on samples of por-Si/SnO _x composites with varying matrix porosity, formed using a powerful ion beam of nanosecond duration, are presented. It is shown that rapid melting and crystallization of the surface leads to the formation of Si nanoparticles with a maximal size of 200 nm. It is established that tin is included in the structure of the nanocomposite in an oxidized state with a small inclusion of metallic β tin. With increasing porosity, the phase composition of the tin nanolayers becomes closer to the state corresponding to the highest tin oxide (SnO₂). It is also shown that, upon an increase in the porosity, the intensity of the tin 4d subvalent line increases, which is, apparently, associated with an enhanced degree of hybridization of tin and oxygen atoms. The changes in the elemental composition of the composite and the depth of tin penetration are estimated from the results of ion etching.     

Influence of vacuum annealing on structures and mechanical properties of Al–Ti–N films deposited by multi-arc ion plating

The Al–Ti–N films deposited by multi-arc ion plating have been annealed in vacuum within the range of 700–1100 °C. X-ray diffraction results showed that the structure of the films underwent the formation of coherent c-TiN and c-AlN for the annealing temperatures were up to 900 °C. A new phase AlTi_x (x = 0.50, 0.56, 3) was observed after annealing. The X-ray photoelectron spectroscopy results showed the intensity of Ti–Al bonds decreased as annealing temperatures increased, indicating the decomposition of (Al, Ti)N into c-TiN and c-AlN were at the expense of Ti–Al bonds. Differential scanning calorimetry experiments were used to investigate the dynamic behavior of the films during annealing process and the results showed that the N₂ formed as a consequence of the phase transformation process. The release of the N₂ resulted in the peeling of the films from the substrates. The film exhibited a maximum hardness of 39 GPa after 900 °C annealing due to the formation of coherent c-TiN and c-AlN phases. In addition, we also investigated the influence of vacuum annealing on adhesive strength.     

Kinetics of the nanocrystalline structure formation

The kinetics of the nanocrystalline structure formation in the Fe_73.5Cu₁Nb₃Si_22.5?xB_x (x=6. 7. 8. 9 at. %) was followed during the annealing runs interrupted between 300 and 700°C.⁵⁷Fe room temperature Mössbauer spectra were taken and complemented by the electrical resistivity and X-Ray diffraction measurements. It has been found that for the 50 K/min temperature increase the formation of the nanocrystalline phase begins above 450°C reaching a maximum around 500°C and is followed by the second stage of crystallization of the disordered intergranular remainder above ca 600°C accompanied by the changes in the occupation of the iron sites in the crystalline α?Fe?Si phase. Thus gained composition-temperature dependence seems to witness for the inhibiting influence of the substitution of B by Si on the crystallization process.     

Electronic structure of the PLD grown mixed phase MoS2/GaN interface and its thermal annealing effect

We report the electronic structure of Molybdenum disulfide (MoS₂) ultrathin 2D films grown by pulsed laser deposition (PLD) on top of GaN/c-Al₂O₃ (0001) substrates annealed up to 550 °C in an ultrahigh vacuum. Our X-ray photoemission spectroscopy (XPS) study shows that the grown films are mixed phase character with semiconducting 2H and metallic 1T phases. After ultrahigh vacuum (UHV) annealing, the 1T/2H phase ratio is significantly modified and film-substrate bonding becomes the leading factor influencing variation of mixed phase compositions. The semiconducting phase is partially transformed to metallic phase by thermal annealing; suggesting that the metallic phase observed here may indeed have more stability compared to the semiconducting phase. The notable enhancement of the 1T/2H ratio induces significant changes in Ga 3d core level spectra taken from bare GaN and MoS₂/GaN sample. The impact of S and/or Mo atoms on the Ga core level spectra is further pronounced with the thermal annealing of grown films. The analysis shows that an enhancement of 1T metallic phase with thermal annealing in MoS₂ layers is manifested by the occurrence of new spectral component in the Ga 3d core level spectra with the formation of Ga-S adlayer interaction through the Ga bonding in defect assisted GaN structure.     

p-type conduction in nitrogen-doped SnO2 films grown by thermal processing of tin nitride films

p-type nitrogen-doped SnO₂ (SnO₂:N) films were grown by thermal processing of amorphous tin nitride films at temperatures between 350 and 500?^°C in flowing O₂?CAr gas mixture. From high-resolution X-ray photoelectron spectroscopy (XPS) and X-ray diffraction patterns, it is deduced that the N atoms replace the O atoms in the SnO₂ lattice. The N dopant is more tightly bound in SnO₂:N at higher thermal oxidation temperatures deduced from the XPS results. The hole concentration obtained at an oxidation temperature of 400?^°C is 1.87×10¹⁹?cm^?3, which is dramatically enhanced compared to previous reports. Our results indicate that the high-temperature thermal oxidation of tin nitride is a facile and effective route to alleviate the self-compensation effect, reduce the content of ??-N₂ double donors, and reinforce the stability of N dopant in the SnO₂:N films.     

A LEELS and auger study of the oxidation of liquid and solid tin

The oxidation of liquid and solid tin from 25 to 240°C has been investigated using 75 eV low energy electron loss spectroscopy (LEELS) and Auger spectroscopy over an oxygen exposure range from zero to 10⁷ L. LEELS was chosen for two reasons. First it can distinguish Sn, SnO and SnO₂ from each other. Second, we show that at 75 eV incident energy LEELS has a penetration depth of only one monolayer. As a result the continuity and stoichiometry of the oxide layer could be studied as a function of thickness from submonolayer to several monolayer thicknesses. Although unable to distinguish SnO from SnO₂ the larger penetration depth of the Auger technique complemented the LEELS study. From zero to one monolayer the oxide grows as islands containing both SnO and SnO₂. Above one monolayer coverage the oxide is continuous and free of metallic tin with its outer most surface enriched in SnO₂. Although oxide films grew more rapidly on polycrystalline tin than on single crystal tin the composition and continuity as a function of thickness remained unchanged. Very little change in oxide growth rate, continuity, or stoichiome- try was observed for solid tin up to temperatures near the melting point. However at 229°C, just 3°C below the melting point of tin, dissolution of oxygen into the metal was observed. A continuous, metal free solid oxide, primarily SnO, could be grown on liquid tin at 240°C than remained stable for 20 min after removal of the oxygen gas. Our model for the early stages of the oxidation of tin is different from that previously proposed on the basis of UPS, XPS, and 400 eV LEELS with respect to the continuity and relative ordering of the SnO and SnO₂ phases. Quantitative comparison of our results with those previously reported shows that the previous results are consistent with our model for the structure and stoichiometry of the initial oxide grown on tin.     

Auger spectroscopic study of the surface composition of Pt/Sn alloys in ultrahigh vacuum and in the presence of oxygen and hydrogen

The surface composition of two Pt/Sn alloys, viz. PtSn and Pt₃Sn, has been followed by means of AES, as a function of annealing in ultrahigh vacuum, oxygen chemisorption and reduction with hydrogen.The results, which were quantitatively interpreted with the aid of a novel calibration technique, reveal the following features: - The surface of PtSn and Pt₃Sn becomes enriched with tin by annealing in vacuum. Ultimate values of 68±5 at% Sn for PtSn and 41±5 at% Sn for Pt₃Sn were attained after annealing at 500°C. - The adsorption of oxygen on the annealed surface of PtSn and Pt₃Sn causes a further enrichment with tin, while severe oxidation of PtSn at 500°C leads to complete disappearance of Pt from the surface. - Oxygen is more strongly and differently bound on a surface containing about 40 at% Sn than on a surface containing about 70 at% Sn. Activated adsorption of oxygen takes place only on the latter. The results suggest the formation of SnO₂ surface complexes on the exposed surface of Pt₃Sn. - Reduction of the alloys at 500°C carries the excess of tin into the bulk and reduces its surface concentration to 35±5 at% for Pt₃Sn and 64±5 at% for PtSn, which is an enrichment of the surface with platinum relative to the annealed state.     

Study of the structural phase transformation,and optical behavior of the as synthesized ZnO–SnO2–TiO2 nanocomposite

Bulk nanocomposites ZnO–SnO₂–TiO₂ were synthesized by solid-state reaction method. The X-ray diffraction patterns and Raman spectra of bulk nanocomposite as a function of sintering temperature (700 °C–1300 °C) indicate that the structural phases of SnO₂ and TiO₂ depend on the sintering temperature while the ZnO retains its hexagonal wurtzite phase at all sintering temperatures and SnO₂ started to transform into SnO at 900 °C and completely converted into SnO at 1100 °C, whereas the titanium dioxide (TiO₂) exhibits its most stable phase such as rutile at low sintering temperature (≤900°C) and it transforms partially into brookite phase at high sintering temperature (≥ 900 °C). The optical band gap of nanocomposite ZnO–SnO₂–TiO₂ sintered at 700 °C, 900 °C, 1100 °C and 1300 °C for 16 hours is calculated using the transformed diffuse reflectance ultra violet visible near infra red (UV–VisNIR) spectra and has been found to be 3.28, 3.29, 3.31 and 3.32 eV, respectively.