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.     

Titanium metallization of alumina ceramics by molten salt reaction

In this work, we reported a novel method that is flexible to metallize alumina ceramics with complex surface. Through Ti²⁺ disproportionation occurred in molten NaCl-KCl-K₂TiF₆ bath, the dense Ti layer was deposited on Al₂O₃ ceramics surface with strong adhesion. The effects of reaction temperature, time and initial K₂TiF₆ concentration on deposition rate were investigated. As-prepared coatings compose of bilayer structure of reactive Ti₂O phase, namely, the outer layer with coarse grains and the inner layer with fine grains. The wettability of eutectic Ag72Cu28 and Pb37Sn63 alloys with metallized Al₂O₃ ceramics was measured by using sessile drop method and compared with that of original ceramics. The results show that the metallized Al₂O₃ surface could be reactively wetted well with Ag72Cu28 and Pb37Sn63 alloys. The contact angles lowered to 35° and 8°, respectively, when temperature rose to 900 °C, showing significant enhancement of wettability after Ti metallization by molten salt reaction.     

ESCA studies of Fe-Ti alloys

Fe-Ti alloys containing 5 to 47% Ti have been studied by ESCA. The alloys were exposed to 0.1 M NaCl for 24 h under open-circuit potential (OCP) during which passive films were formed. The passive film consisted of FeO and TiO₂ in the inner layer while Fe₂O₃, water, and hydroxyl groups were present in the outermost monolayers, irrespective of composition. The thickness of the passive layer was reduced from 4.4 nm to 1.0 nm with increasing Ti content. The amount of iron oxide in the passive layer also decreased with increasing Ti. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Alloys with 5–28% Ti showed a relatively high corrosion rate but that with 47 wt.% Ti had a much lower corrosion rates.     

Structure of Al2O3 thin layers synthesized on the silicon surface by atomic layer deposition

The distribution of the phase and chemical composition at an Al₂O₃/Si interface is studied by depth-resolved ultrasoft x-ray emission spectroscopy. The interface is formed by atomic layer deposition of Al₂O₃ films of various thicknesses (from several to several nanometers to several hundreds of nanometers) on the Si(100) surface (c-Si) or on a 50-nm-thick SiO₂ buffer layer on Si. L _2,3 bands of Al and Si are used for analysis. It is found that the properties of coatings and Al₂O₃/Si interfaces substantially depend on the thickness of the Al₂O₃ layer, which is explained by the complicated character of the process kinetics. At a small thickness of coatings (up to 10–30 nm), the Al₂O₃ layer contains inclusions of oxidized Si atoms, whose concentration increases as the interface is approached. As the thickness increases, a layer containing inclusions of metallic Al clusters forms. A thin interlayer of Si atoms occurring in an unconventional chemical state is found. When the SiO₂ buffer layer is used (Al₂O₃/SiO₂/Si), the structure of the interface and the coating becomes more perfect. The Al₂O₃ layer does not contain inclusions of metallic aluminum, does not vary with the sample thickness, and has a distinguished boundary with silicon.     

Luminescence characterisation of alumina substrates using cathodoluminescence microscopy and spectroscopy

Polycrystalline alumina (Al₂O₃) substrates, found in many electronic devices and proposed as dosemeters in emergency situations, were invstigated using a scanning electron microscope (SEM) equipped with cathodoluminescence (CL) and elemental analysis probes. The characteristics of the CL spectra, surface morphology, and impurity content of the Al₂O₃ substrates were examined and compared with those of single crystal dosimetry-grade Al₂O₃:C. Whereas the CL spectrum, measured from 250 to 800 nm, for the Al₂O₃:C, contained resolved bands located at ∼340 nm and at ∼410 nm, the spectrum measured with the Al₂O₃ substrate was significantly broader, extending from ∼250 to ∼450 nm, and also included a narrow band at 695 nm. While it is likely that the accepted model of recombination at F⁺ (∼340 nm) and F (∼410 nm) in Al₂O₃:C also applies to the substrate, it is suggested that the presence of impurities within the alumina give rise to additional recombination centres. The 695 nm emission has been assigned to a Cr³⁺ ion impurity in previous work on alumina and a band indicated at ∼300 nm may be associated with Mg²⁺ or Ca²⁺_, the presence of which was confirmed by elemental mapping. Comparison of the spatial distribution of CL with the surface morphology and elemental composition of the samples indicates that the components of the emission spectrum can be qualitatively correlated with impurity content and morphological features of the samples.     

Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

X-ray spectral analysis of the interface of a thin Al<Subscript>2</Subscript>O<Subscript>3</Subscript> film prepared on silicon by atomic layer deposition

The extent and phase chemical composition of the interface forming under atomic layer deposition (ALD) of a 6-nm-thick Al₂O₃ film on the surface of crystalline silicon (c-Si) has been studied by depthresolved, ultrasoft x-ray emission spectroscopy. ALD is shown to produce a layer of mixed Al₂O₃ and SiO₂ oxides about 6–8 nm thick, in which silicon dioxide is present even on the sample surface and its concentration increases as one approaches the interface with the substrate. It is assumed that such a complex structure of the layer is the result of interdiffusion of oxygen into the layer and of silicon from the substrate to the surface over grain boundaries of polycrystalline Al₂O₃, followed by silicon oxidation. Neither the formation of clusters of metallic aluminum near the boundary with c-Si nor aluminum diffusion into the substrate was revealed. It was established that ALD-deposited Al₂O₃ layers with a thickness up to 60 nm have similar structure.     

氧化铝与Al(100)基体间界面原子结构研究

本文介绍了用MeV离子散射和沟道效应研究单晶铝表面无定型氧化层与基体之间界面原子结构的方法。报道了Al₂O₃/Al(100)界面原子结构的实验结果。实验表明,在纯氧气氛围中400℃下生成的氧化铝膜,铝和氧原子浓度比例严格为2与3之比;Al₂O₃膜和Al(100)基体之间的界面极其陡峭,氧化铝膜下Al(100)基体表面的再构层不大于一个原子层。由实验测量与用Monte Carlo方法计算结果比较,得到再构层原子离开原来晶 关键词：     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

Synthesis of copper alloys with extended solid solubility and nano Al2O3 dispersion by mechanical alloying and equal channel angular pressing

Cu–4.5 wt % Cr and Cu–4.5 wt % Cr–3 wt % Ag alloys, with and without nanocrystalline Al₂O₃ dispersions (particle size <10 nm), were synthesized by mechanical alloying/milling and consolidated by equal-channel angular pressing (ECAP) at ambient temperature. Microstructural characterization and phase analysis by X-ray diffraction, as well as scanning and transmission electron microscopy, provided evidence for the formation of a Cu-rich extended solid solution with nanometric (<30 nm) crystallite size after 25 h of milling, with uniformly dispersed alumina nanoparticles embedded in it. Consolidation of Cu–4.5 wt % Cr–3 wt % Ag alloy with 10 wt % nanocrystalline Al₂O₃ by eight ECAP passes was shown to result in a composite with an exceptionally large hardness of 390 VHN and enhanced wear resistance. The electrical conductivity of the pellets of the latter alloy without Al₂O₃ is about 30% IACS (international annealing copper standard), whereas pellets with 5 or 10 wt % Al₂O₃ dispersion exhibit a conductivity of about 20–25% IACS. Thus, the present room temperature synthesis and consolidation route appear to offer a promising avenue for developing high-strength, wear/erosion-resistant Cu-based electrical contacts with nano-ceramic dispersion.     

Optimized emitter contacting on multicrystalline silicon thin film solar cells

We present an optimized contacting scheme for multicrystalline silicon thin film solar cells on glass based on epitaxially crystallized emitters with a thin Al₂O₃ layer and a silver back reflector. In a first step a 6.5 µm thick amorphous silicon absorber layer is crystallized by a diode laser. In a second step a thin silicon emitter layer is epitaxially crystallized by an excimer laser. The emitter is covered by an Al₂O₃ layer with a thickness ranging from 1.0 nm to 2.5 nm, which passivates the surface and acts as a tunnel barrier. On top of the Al₂O₃ layer a 90–100 nm thick silver back reflector is deposited. The Al₂O₃ layer was found to have an optimal thickness of 1.5 nm resulting in solar cells with back reflector that achieve a maximum open‐circuit voltage of 567 mV, a short‐circuit current density of 27.9 mA/cm², and an efficiency of 10.9%. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Silicon solar cells with Al2O3 antireflection coating

The paper presents the possibility of using Al₂O₃ antireflection coatings deposited by atomic layer deposition ALD. The ALD method is based on alternate pulsing of the precursor gases and vapors onto the substrate surface and then chemisorption or surface reaction of the precursors. The reactor is purged with an inert gas between the precursor pulses. The Al₂O₃ thin film in structure of the finished solar cells can play the role of both antireflection and passivation layer which will simplify the process. For this research 50×50 mm monocrystalline silicon solar cells with one bus bar have been used. The metallic contacts were prepared by screen printing method and Al₂O₃ antireflection coating by ALD method. Results and their analysis allow to conclude that the Al₂O₃ antireflection coating deposited by ALD has a significant impact on the optoelectronic properties of the silicon solar cell. For about 80 nm of Al₂O₃ the best results were obtained in the wavelength range of 400 to 800 nm reducing the reflection to less than 1%. The difference in the solar cells efficiency between with and without antireflection coating was 5.28%. The LBIC scan measurements may indicate a positive influence of the thin film Al₂O₃ on the bulk passivation of the silicon.     

Characterization of a bioactive nanotextured surface created by controlled chemical oxidation of titanium

Events at bone-implant interfaces are influenced by implant surface properties. Our previous work has revealed that osteogenic activity is enhanced by a nanotextured Ti surface, obtained by controlled chemical oxidation using a H₂SO₄/H₂O₂ mixture. To better understand the origin of this biological effect, we have carried out a characterization of the modified surface at the nanoscale. In particular, the morphology, structure, and chemical composition of the Ti surface were examined thoroughly. X-ray photoelectron spectroscopy (XPS), combined with grazing-angle Fourier-transform infrared (FTIR) spectroscopy, revealed that the oxidized Ti surface consists of almost pure TiO₂ with Ti:O ratio ranging between 1:2.02 and 1:2.08. Raman spectroscopy and X-ray diffraction (XRD) indicated that the chemically treated Ti surface is mainly composed of amorphous titania. Scanning electron microscopy (SEM) clearly showed that the treated Ti substrate becomes highly porous and has a surface consisting of nano-sized pits, which have average diameters and fractal dimensions ranging between 20-22 nm and 1.11-1.17, respectively. Atomic force microscopy (AFM) revealed a three-fold increase in surface roughness. The thickness of the oxide layer on the treated Ti surface is estimated to be ∼32-40 nm. Together, these observations provide a detailed characterization of chemically oxidized Ti surfaces at the nanoscale and offer new prospects for understanding and controlling the relationship between the properties of materials and their interactions with cells. Our work brings us closer to the creation of “intelligent” implant surfaces, capable of selectively influencing cell behavior.     

Nanoscale Analysis of Multilayer Interfaces of W/Al2O3/Ti/Cu

W, Al₂O₃ and Ti films were deposited onto a Cu substrate by means of the rf magnetron sputtering method. After deposition, the foils were annealed at various temperatures in vacuum and the interfaces of the films were observed by a field-emission transmission electron microscopy (FE-TEM), after preparing a cross-sectional thin foil using a focused ion beam (FIB) machine. After annealing the foil at 473 and 623 K, no reaction phases were identified at each interface of W/Al₂O₃, Al₂O₃/Ti and Ti/Cu-substrate. However, from the results of compositional analysis at the interface of Al₂O₃/Ti bilayer, after heat-treatment at 623 K, the formation of an oxide layer was suggested even though it was not clearly observed. On the other hand, after heat-treatment at 823 K, the formation of CuTi₂, Cu₃Ti₂ and Cu₄Ti phases were identified at the interface of Ti/Cu bilayers from the compositional analysis of reaction layers after heat-treatment at different temperatures, and the diffusion coefficients and activation energies in the phases were evaluated. In this paper, the influence of heat-treatment on the interfacial behavior of multilayer are discussed on the basis of nanoscale analysis by EDS and HRTEM images.     

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al₂O₃) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al₂O₃ core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al₂O₃ formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.     

Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al₃Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi₃ were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.     

Effect of magnesium addition on the wetting of alumina by aluminium

In this report the wetting behaviour between polycrystalline alumina substrates and molten aluminium doped with magnesium as a wetting agent has been studied using the sessile drop technique. The time required for equilibrium attainment is investigated. To explore the formation of possible phases at the interface, electron microscopic studies along with EDX analysis have been employed. It is found that magnesium reduces the time and temperature required for equilibrium in the Al/Al₂O₃ system. The Al-7 wt% Mg and Al-10 wt% Mg alloys can wet alumina at temperatures as low as 900 °C. It is also found that molten aluminium doped with magnesium can wet polycrystalline alumina at temperatures below 1000 °C. A thin reaction layer was observed at the Al-Mg/Al₂O₃ interface in the present study.     

Novel and low reflective silicon surface fabricated by Ni-assisted electroless etching and coated with atomic layer deposited Al2O3 film

In this paper, nickel nanoparticles (Ni NPs) were deposited on planar silicon and pyramidal silicon wafers by the magnetron sputtering method, and then these Ni NP-covered samples were etched in a hydrofluoric acid, hydrogen peroxide, and deionized water mixed solution at room temperature to fabricate a low reflective silicon surface. An alumina (Al₂O₃) film was then deposited on the surface of the as-etched pyramidal sample by atomic layer deposition to further reduce the reflectance. The morphologies and compositions of these samples were studied by using a field emission scanning electron microscope attached to an energy-dispersive X-ray spectrometer. The surface reflectance measurements were carried out with a UV-Vis-NIR spectrophotometer in a wavelength range of 200–1100 nm. The SEM images show that the as-etched planar and pyramidal silicon samples were covered with many rhombic nanostructures and that some nanostructures on the planar silicon surface were ready to exhibit a flower-like burst. The reflectances of the as-etched planar and pyramidal silicon samples were 5.22 % and 3.21 % in the wavelength range of 400–800 nm, respectively. After being coated with a 75-nm-thick Al₂O₃ film, the etched pyramidal silicon sample showed an even lower reflectance of 2.37 % from 400 nm to 800 nm.     

Evolution of the interfacial phases in Al2O3–Kovar® joints brazed using a Ag–Cu–Ti-based alloy

Abstract

A systematic investigation of the brazing of Al₂O₃ to Kovar^® (Fe–29Ni–17Co wt.%) using the active braze alloy (ABA) Ag–35.25Cu–1.75Ti wt.% has been undertaken to study the chemical reactions at the interfaces of the joints. The extent to which silica-based secondary phases in the Al₂O₃ participate in the reactions at the ABA/Al₂O₃ interface has been clarified. Another aspect of this work has been to determine the influence of various brazing parameters, such as the peak temperature, T_p, and time at T_p, τ, on the resultant microstructure. As a consequence, the microstructural evolution of the joints as a function of T_p and τ is discussed in some detail. The formation of a Fe₂Ti layer on the Kovar^® and its growth, along with adjacent Ni₃Ti particles in the ABA, dominate the microstructural developments at the ABA/Kovar^® interface. The presence of Kovar^® next to the ABA does not change the intrinsic chemical reactions occurring at the ABA/Al₂O₃ interface. However, the extent of these reactions is limited if the purity of the Al₂O₃ is high, and so it is necessary to have some silica-rich secondary phase in the Al₂O₃ to facilitate the formation of a Ti₃Cu₃O layer on the Al₂O₃. Breakdown of the Ti₃Cu₃O layer, together with fracture of the Fe₂Ti layer and separation of this layer from the Kovar^®, has been avoided by brazing at temperatures close to the liquidus temperature of the ABA for short periods of time, e.g., for T_p between 820 and 830 °C and τ between 2 and 8 min.