Influence of annealing temperature on structural, optical and magnetic properties of Zn0.95Cu0.02Cr0.03O powders

Zn_0.95Cu_0.02Cr_0.03O powders have been synthesized by the sol-gel method and sintered in argon atmosphere under different temperatures. The structural, optical and magnetic properties of the powders were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and vibrating sample magnetometer (VSM). The XRD results demonstrated that Cr and Cu ions are incorporated into ZnO successfully when annealing temperatures were 600 and 700 °C. But when the samples were annealed at 500 °C, the crystallinity of the samples was not very good. However, when the annealing temperature was increased to 800 °C, the secondary phase of Cu and ZnCr₂O₄ appeared in the samples. The PL spectra revealed that the position of the ultraviolet (UV) emission peak of the samples showed a blue shift and the green emission peak enhanced significantly with the annealing temperature increasing from 600 to 700 °C. Magnetic measurements indicated that the room temperature ferromagnetism of Zn_0.95Cu_0.02Cr_0.03O was intrinsic in nature. In addition, the saturation magnetization (Ms) increased from 0.0078 to 0.0088 emu/g with the annealing temperature increased from 600 to 700 °C.     

Control of crystallographic orientation in L10 FePt films by using Cr and CrW underlayers

The microstructure and magnetic properties of FePt films grown on Cr and CrW underlayers were investigated. The FePt films that deposited on Cr underlayer show (2 0 0) orientation and low coercivity because of the diffusion between FePt and Cr underlayer. The misfit between FePt magnetic layer and underlayer increases by small addition of W element in Cr underlayer or using a thin Mo intermediate layer, which is favorable for the formation of (0 0 1) orientation and the transformation of FePt from fcc to fct phase. A good FePt (0 0 1) texture was obtained in the films with Cr₈₅W₁₅ underlayer with substrate temperature of 400 °C. The FePt films deposited on Mo/Cr underlayer exhibit larger coercivity than that of the films grown on Pt/Cr₈₅W₁₅ because 5 nm Mo intermediate layer depressed the diffusion of Cr into magnetic layer.     

A high-throughput search for direct methanol fuel cell anode electrocatalysts of type PtxBiyPbz

We used a high-throughput method to screen for direct methanol fuel cell anode electrocatalysts in the Pt-Bi-Pb system. Previous studies showed that PtBi and PtPb (both NiAs structure type) were active electrocatalysts for the oxidation of formic acid, but only PtPb was active in oxidizing methanol. We synthesized thin films with continuous composition spreads of the three elements by magnetron sputtering at deposition temperatures from ambient to 510 °C. A fluorescence method was then used to identify compositions that were active toward methanol oxidation. Only films deposited between temperatures of 160 and 400 °C showed electrocatalytic activity. The areas that were active for methanol oxidation showed predominantly the NiAs structure type according to XRD, with optimal activity for compositions near PtBi_0.01Pb_0.53.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Characterization of SnO2 obtained from the thermal oxidation of vacuum evaporated Sn thin films

Tin oxide has been prepared by thermal oxidation of evaporated tin thin films onto pyrex glass substrates. Films oxidation was achieved in air at a temperature of 600 °C with varied duration from 20min to 3 h. Structural, optical and electrical properties of the films were characterized by means of X-ray diffraction, UV–vis spectroscopy and electrical resistivity measurements respectively. The X-ray analysis revealed the transformation of Sn into SnO₂ with preferential orientation along (101) plans. No intermediate phases such as SnO and Sn₃O₄ were evidenced. It was also found that the SnO₂ crystallites orientation changed with the annealing time due to the strain energy effect. Both band gap energy and electrical resistivity decrease with annealing time due to the crystalline quality improvement and films densification. We have noticed that oxidation at 600 °C for 3 h leads to transparent and conductive films with suitable properties for photovoltaic applications.     

Low temperature deposited Zr-B film applicable to extremely thin barrier for copper interconnect

We have prepared thin Zr-B films at low temperatures as a new material applicable to an extremely thin barrier against Cu diffusion in Si-ULSI metallization. The obtained Zr-B films mainly consist of the ZrB₂ phase with a nanocrystalline texture on SiO₂ and a fiber texture on Cu. The resistivity of the Zr-B films depends on the substrate of SiO₂ or Cu. The constituent ratio of B/Zr is almost 2, though the contaminants of oxygen, nitrogen, and carbon are incorporated in the film. The nanocrystalline structure of the Zr-B film on SiO₂ is stable due to annealing at temperatures up to 500 °C for 30 min. We applied the 3-nm thick Zr-B film to a diffusion barrier between Cu and SiO₂, and the stable barrier properties were confirmed. We can demonstrate that the thin Zr-B film is a promising candidate for thin film application to a metallization material in Si-ULSIs.     

Structural characterizations of Co2MnSi/MgO/Co2MnSi magnetic tunnel junctions by transmission electron microscopy

We have investigated the structure of Co₂MnSi/MgO/Co₂MnSi magnetic tunneling junctions with different tunnel magnetoresistance values depending on the in situ annealing temperatures just after the deposition of the upper Co₂MnSi electrodes. The nano-beam diffraction patterns indicated that the degree of order of the upper Co₂MnSi electrode annealed at 550 °C was higher than that of an electrode annealed at 400 °C. Moreover, the degree of the L2₁ order of the upper Co₂MnSi electrode annealed at 550 °C was even lower than that of the lower Co₂MnSi electrode annealed at an almost equal temperature of 600 °C. Atomic-scale observation using a high-angle annular dark-field (HAADF) method distinctly showed the existence of the L2₁-ordered regions in the B2-ordered matrix in the upper Co₂MnSi electrode annealed at 400 °C.     

Xenon-beam-induced atomic transport through Cr/Al and Cr2N/Al interfaces

Cr layers (60–75 nm) on Al substrates and Cr₂N layers (40–120 nm) on Al+3 wt.% Mg substrates were irradiated at 80 K and 300 K with 150–900 keV Xe-ions. The ion-beam-induced interface mixing was analyzed by means of Rutherford Backscattering Spectrometry (RBS). Both systems exhibit fairly small mixing rates, with those of Cr/Al being enhanced at 300 K target temperature, due to radiation-enhanced diffusion. The observed interface broadening is compared with predictions of ballistic and thermal spike mixing models. The low-temperature mixing rates in the system Cr/Al are underestimated by the ballistic model, but are rather well reproduced by local spike models. Mixing in the Cr₂N/Al system at both temperatures, on the other hand, seems to be rather well described by the ballistic model.     

Structural evolution of sol-gel SiO2 heated glasses containing silver particles

SiO₂ based glasses added with nanometric-silver particles have been prepared by the traditional sol-gel process, using the tetraethyl-orthosilicate alkoxide. The Ag particles were prepared using a new method described in this article, the method uses a cementation reaction between Ag ions and an iron electrode. The size of the particles, measured in the dried glass, was in the range of 100-200 nm. The observed structural changes depend on the annealing conditions, such as the annealing temperature, the amount of silver particles and the type of acid (HCl or HNO₃) used to catalyze the hydrolysis/condensation reactions during the sol-gel process. Samples prepared using both acids crystallized into the cristobalite phase after thermal annealing at 800 °C. The amount of SiO₂ crystallized depends on the amount of Ag present in the glass. Samples prepared from solutions catalyzed with HCl acid show the formation of nanometric Ag particles after thermal annealing at 500 °C, these small particles are not observed after similar treatments when HNO₃ is used as the catalytic acid. HCl and Ag₂O form AgCl which is reduced by residual carbon to form Ag ultrafine particles. The diffusion of the reduced Ag spices, which form these particles, is facilitated by the opened structure of the glasses added with Ag, as indicated by IR measurements.     

Zn incorporation and (CuIn)1−xZn2xSe2 thin film formation during the selenization of evaporated Cu and In precursors on Al:ZnO coated glass substrates

CuInSe₂ thin films with typical 1.0 eV gap energy and tetragonal chalcopyrite structure have been obtained on soda–lime glass substrates by the reaction of sequentially evaporated Cu and In layers with elemental selenium vapor, at 500 °C in flowing Ar. When analogous deposition and reaction processes were performed on Al:ZnO coated glasses, some increment in the band gap energy and diminution in the crystalline interplanar spacings have been detected for the resulting films with an extent that depends on the Cu/In atomic ratio of the evaporated precursor layers. This fact has been related to Zn incorporation into the selenized film, with quaternary (CuIn)_1−xZn_2xSe₂ compound formation that is influenced by the presence of copper selenide phases during the reaction process. Such deductions are supported by the optical, structural and compositional characterizations that have been performed comparatively on samples prepared by selenization of evaporated metallic precursors with two different Cu/In ratios (0.9 and 1.1) on bare and Al:ZnO coated glass substrates.     

Investigation on FR(LT)–FR(HT) phase transition and pyroelectric properties of pulsed laser deposited Pb(Zr0.93Ti0.07)O3 thin films

The preparation process, crystallinity and electrical properties of pulse laser deposited Pb(Zr_xTi_1−x)O₃ (PZT) thin films were investigated in this paper. PZT (x = 0.93) thin film samples deposited at different substrate temperatures were prepared. Si (1 1 0) was the substrate; Ag and YBCO were the top electrode and the bottom electrode respectively. The bottom electrode YBCO was deposited on the Si substrate by pulsed laser deposition (PLD), and then PZT was epitaxially deposited on YBCO also by PLD. After annealing, the top electrode Ag was prepared on PZT by thermal evaporation, and then the Ag/PZT/YBCO/Si structured thin films were obtained. The XRD and the analysis of their electrical characters showed that, when the substrate temperature was elevated from 600 °C to 800 °C, the crystallinity and electrical properties of PZT thin films became better and better, and the F_R(LT)–F_R(HT) phase transition of PZT (x = 0.93) thin films occurred at 62 °C. The PZT film deposited at 800 °C had the best pyroelectric properties, and when the F_R(LT)–F_R(HT) phase transition of this film occurred, the peak value of pyroelectric coefficient (p) was obtained, with a value of 1.96 × 10⁻⁶ C/(cm² K). The PZT film deposited at 800 °C had the highest remnant polarization (P_r) and the lowest coercive field (E_c), with the values of 34.3 μC/cm² and 41.7 kV/cm respectively.     

Study of solid-state reactions in Sm(Co,Fe, Cu,Zr)z 2:17-type alloys by means of in situ electrical resistivity measurements

In the present work, solid-state reactions in Sm₂(Co, Fe, Cu, Zr)₁₇-type alloys have been investigated by means of in situ electrical resistivity measurements. Changes in the electrical resistivity of a Sm(Co_0.74Fe_0.1Cu_0.12Zr_0.04)_8.5 alloy after solid solution treatment at 1190 °C, quenching to room temperature, and during isothermal ageing at temperatures between 400 and 900 °C, have indicated microstructural/phase changes occurring at temperatures below those commonly used for the development of high coercivity in Sm(Co, Fe, Cu, Zr)_z-type materials. Subsequent crystallographic and magnetic transition measurements have shown a high degree of correlation with respect to the changes observed in the electrical resistivity during isothermal ageing.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

XPS and ToF-SIMS analysis of natural rubies and sapphires heated in an inert (N2) atmosphere

Advanced surface analysis techniques: X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, have been employed in the study of heat treatment of natural corundum as ruby and sapphire. The stones were heat treated in an inert (N₂) atmosphere. The setting temperatures were: 1000, 1100, 1200, 1300, 1400, 1500 and 1600 °C. The XPS studies and the parallel ToF-SIMS experiments revealed diffusion behavior of Fe and Ti in the as-mined stones as evidenced by surface observations. Both metals exhibited broad maxima in surface concentration near 1300 °C. Owing to its superlative detection limit, ToF-SIMS spectra are able to provide the temperature-dependent concentration profiles of trace transition metals such as Cr, Cu and V at a level not detectable by XPS. Visible appearance of the stones is clearly affected by heat treatment. Interestingly, the ruby stones did not exhibit cloudy inclusion (“silk”) on heating, contrary to previous experiments under atmospheric conditions.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

Surface morphology and the phase formation at Cr/Si system

Metal silicide technology has been attracting attention worldwide and it constitutes an active, frontier area of research. Research in this area has not only stimulated the exploration of new phenomena, but is also leading to a technological revolution. Electron beam evaporation in ultra high vacuum (UHV) environment is one of the best techniques to grow thin metal film on Si substrate. Metal silicide contact is an interesting and important part of integrated circuit. Due to selective growth and high thermal stability metal silicides are used in very large scale integrated (VLSI) and ultra large scale integrated (ULSI) applications. In this paper our interest is to show GIXRD, XRR and SPM measurement on C (2 nm)/Cr (25 nm)/Si (1 0 0) system in which thin films were deposited using electron beam evaporation technique at 2 × 10⁻⁸ Torr vacuum. The capping layer of 2 nm carbon is deposited to stop contamination. The C (2 nm)/Cr (25 nm)/Si (1 0 0) system were annealed in 10⁻⁵ Torr vacuum at temperatures 300-600 °C to study the formation of chromium silicide. Structural properties at the interface has been studied by grazing incidence X-ray diffraction (GIXRD), which shows formation of Cr₃Si and CrSi₂ as a result of interface mixing due to annealing. The morphology of the system was investigated by AFM in tapping mode. It was found that nano-rod type structures were formed with annealing at 600 °C temperature.     

Correlation between crystallinity and resistive switching behavior of sputtered WO3 thin films

The as-deposited WO₃ thin films were post-annealed at different temperatures (300 °C and 600 °C) in air to investigate a correlation between crystallinity and switching behavior of WO₃ thin films. Associating the results of XRD, FTIR, XPS and FESEM measurements, the annealing-caused crystallinity change contributes to the variation of the switching behaviors of the WO₃ thin films. The as-deposited WO₃ films with low crystalline structure are preferred for random Ag conducting path, resulting in large switching ratio but fluctuating I–V hysteresis, whereas the annealed WO₃ films with crystallized compact structure limits Ag conducting path, favoring the stable I–V hysteresis but small switching ratio. It is therefore concluded that electrochemical redox reaction-controlled resistance switching depends not only on electrode materials (inert and reactive electrodes) but also on crystallinity of host oxide.     

Catalysis, by amorphous carbon, of H2 attack on oxidized U-0.1 wt% Cr surfaces

Amorphous carbon, evaporated on a thin oxide layer covered U-0.1 wt% Cr sample, was proven to significantly catalyze H₂ reaction with the metal. A hydride was formed preferentially on the carbon-covered surface, for vacuum pretreatment temperatures of 150 and 190 °C and hydrogen reactions of 150 and 90 °C, respectively. Dependence of the reaction rate on the thickness of the layer was observed.     

Fabrication and characterization of CuO-core/TiO2-shell one-dimensional nanostructures

We have fabricated CuO-core/TiO₂-shell one-dimensional nanostructures by coating the CuO nanowires with MOCVD-TiO₂. The structure of the core/shell nanowires has been investigated by using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction analysis techniques. The CuO-cores and the TiO₂-shells of the as-synthesized nanowires have been found to have crystalline monoclinic CuO and crystalline tetragonal anatase TiO₂ structures, respectively. The CuO-core/TiO₂-shell nanowires are winding and has rougher surface, whereas the CuO nanowires are straight and have smoother surface.Influence of the substrate temperature and the growth time on the structure such as the morphology, size, and crystallographic orientation of CuO nanowires synthesized by thermal oxidation of Cu foils have also been investigated. All the nanowires have only the CuO phase synthesized at 600 °C, whereas those synthesized at 400 °C have both CuO and Cu₂O phases. The highest density of CuO nanowires with long thin straight morphologies can be obtained at 600 °C. In addition, the growth mechanism of the CuO nanowires has been discussed.