The effect of Ti on the wetting of CaF<Subscript>2</Subscript> substrate by In–Ti and Ga–Ti alloys. Ab-initio consideration

CaF₂ is a thermodynamically stable, non-reactive compound, displaying a relatively high contact angle with pure liquid metal melts. A remarkable decrease of this contact angle takes place when small amounts of Ti are added to liquid In (a decrease from 125 to 20°) or to liquid Ga (from 118 to 60°). Thermodynamic analysis indicates that this feature cannot be attributed to chemical reactions between the substrate and the melt. It was suggested that the reason for this behavior may be a preferential titanium adsorption from the liquid In–Ti or Ga–Ti solution at the substrate surface. In order to understand the nature of the In–Ti or Ga–Ti bonding in the vicinity of the CaF₂ surface, the adsorption energy of 0.5 monolayer of In and Ga was computed for three different surface conditions: (i) clean CaF₂(111), (ii) CaF₂(111) with In or Ga adatoms, and (iii) CaF₂(111) with Ti adatoms. The differences in adsorption energies for these configurations are related to the electron charge redistribution in the vicinity of the interface, and to the density of states of the electronic subsystems. It was found that the adsorption energy of In or Ga increases due to the lateral interactions with the adatoms. According to the analysis, a strong lateral interaction exists between Ti adatoms and Me, while relatively weak interaction exists between Me and Me adatoms. The difference of the lateral interactions was considered in order to explain the improvement of the wetting of CaF₂ substrate by Ti alloying of In and Ga.     

Theoretical prediction of the structural,elastic, electronic and thermodynamic properties of V3M (M = Si,Ge and Sn) compounds

Density functional theory (DFT), is used in our calculations to study the V₃M (M = Si, Ge and Sn) compounds, we are found that V₃Sn compound is mechanically unstable because of a negative C₄₄ = −19.41 GPa. For each of these compounds considered, the lowest energy structure is found to have the lowest N(E_f) value. Also there is a strong interaction between V and V, the interaction between M (M = Si, Ge, Sn) and V (M and M) is negative, not including Si [Sn]. In phonon density of states PDOS, the element contributions varies from lighter (high frequency) to heaviest (low frequency).     

Adsorption effect in non-reaction wetting: In–Ti on CaF2

The experiments show that the alloying liquid In with only (0.1–0.5) at% Ti dramatically reduces the equilibrium contact angle Θ _∞ formed by In on the surface of CaF₂. The aim of this paper is to clarify whether this practically important and conceptually challenging effect can be explained solely by Ti adsorption at the F-terminated solid–liquid interface without resorting to any other Ti-induced effect. The combination of ab initio calculations and regular solution approximation was proposed for finding the binding energy, ΔE _Ti of Ti adatom with the interface “CaF₂/liquid solutions In–Ti.” With thus obtained ΔE _Ti=1.16 eV, we calculated from the Shishkovsky isotherm the reduction in the solid–liquid interface energy, Δγ _SL induced by Ti adsorption from liquid In with various Ti concentration, C. It was found that Δγ _SL(C) dependence demonstrated close inverse correspondence with Θ _∞(C) and that the theory fitted very well all available experimental data on the concentration and temperature dependence of Δγ _SL. It was concluded that the Ti adsorption effect is large enough to account for the observed wetting improvement. The proposed multiscale modeling approach to the role of adsorption in wetting can be applied also to other nonreactive systems “liquid metal–ceramics” where the substrate determines the surface density of the adsorption sites for the active element.     

Characterisation of Interfaces Between Liquid Tin and Alumina in the Presence of Titanium Alloy Additions

Neutron reflection spectroscopy has been used to characterise the composition of interfaces between liquid Sn-Ti alloys and Al₂O₃. The reflectivity profiles for both 1% and 3% Ti alloys are consistent with the presence of a layer approximately 2 nm thick at the liquid/solid interface, showing extensive segregation of Ti. The composition of this layer is not pure Ti but shows a greater Ti content than any known Ti oxide composition. In all interfaces exposed to liquid metals at elevated temperature (including pure Sn) there is a layer of thickness 20–100 nm on the alumina surface with slightly lower neutron scattering length density than pure alumina. This is interpreted as evidence for surface roughening of the Al₂O₃ surface during exposure to the liquid metal.     

Ionic potential analysis of RHEED rocking curves from fluoride structures

Rocking curves of reflection high energy electron diffraction from MnF₂ and CaF₂(1 1 1) surfaces have been calculated with ionic scattering potentials. The potentials were derived from tabulated X-ray scattering factors and expressed in the Doyle-Turner representation. The Coulomb potential of the ions was introduced into the calculations of diffracted intensity using dynamical diffraction theory. Comparison of the calculated and measured rocking curves for CaF₂(1 1 1) surface confirmed that it is bulk terminated; the correction to volume average potential was found to be 1.1 eV (much less than when using atomic potentials). Analysis of the rocking curves from ultra-thin MnF₂ layers on CaF₂(1 1 1) indicated that MnF₂ inherits the cubic lattice of fluorides up to a thickness of three molecular layers.     

Quantitative determination of the local structure of H2O on TiO2(1 1 0) using scanned-energy mode photoelectron diffraction

O 1s scanned-energy mode photoelectron diffraction has been used to determine the local structure of molecular water on TiO₂(1 1 0). The adsorption site is found to be atop five-fold coordinated surface Ti atoms, confirming the results of published total energy calculations and STM imaging. The Ti-O_w bondlength is found to be 2.21 ± 0.02 Å, much longer than Ti-O bondlengths in bulk TiO₂ and for the formate (HCOO-) species adsorbed on this surface. This is consistent with relatively weak bonding, and in general agreement with total energy calculations, although all of the published calculations yield bondlengths somewhat longer than the experimental value. Structural optimisation based on the photoelectron diffraction data also provides some information on the associated substrate relaxation. In particular, the bondlength of the five-fold coordinated surface Ti atom to the O atom directly below shows the same contraction (relative to the bulk) as is found for the clean surface, reinforcing the picture of rather weak bonding of the water to this same Ti surface atom.     

Electrical, structural and surface morphological properties of thermally stable low-resistance W/Ti/Au multilayer ohmic contacts to n-type GaN

A W/Ti/Au multilayer scheme has been fabricated for achieving thermally stable low-resistance ohmic contact to n-type GaN (4.0 × 10¹⁸ cm⁻³). It is shown that the as-deposited W/Ti/Au contact exhibits near linear I-V behaviour. However, annealing at temperature below 800 °C the contacts exhibit non-linear behaviour. After annealing at a temperature in excess of 850 °C, the W/Ti/Au contact showed ohmic behaviour. The W/Ti/Au contact produced specific contact resistance as low as 6.7 × 10⁻⁶ Ω cm² after annealing at 900 °C for 1 min in a N₂ ambient. It is noted that the specific contact resistance decreases with increase in annealing temperature. It is also noted that annealing the contacts at 900 °C for 30 min causes insignificant degradation of the electrical and thermal properties. It is further shown that the overall surface morphology of the W/Ti/Au stayed fairly smooth even after annealing at 900 °C. The W/Ti/Au ohmic contact showed good edge sharpness after annealing at 900 °C for 30 min. Based on the Auger electron spectroscopy and glancing angle X-ray diffraction results, possible explanation for the annealing dependence of the specific contact resistance of the W/Ti/Au contacts are described and discussed.     

Adsorption of ethene on Pt(1 1 1) and ordered PtxSn/Pt(1 1 1) surface alloys: A comparative HREELS and DFT investigation

The adsorption of ethene (C₂H₄) on Pt(1 1 1) and the Pt₃Sn/Pt(1 1 1) and Pt₂Sn/Pt(1 1 1) surface alloys has been investigated experimentally by high-resolution electron energy loss spectroscopy and temperature programmed desorption. The experimental results have been compared with density functional theory (DFT) calculations allowing us to perform a complete assignment of all vibration modes and loss features to the species present on the surfaces. On Pt(1 1 1) as well as on the Pt-Sn surface alloys an η² di-σ-bonded conformation of ethene has been found to be the most stable adsorbed form. In addition to this majority species a minor amount of π-bonded ethene has been identified, which is more abundant on the Pt₂Sn surface alloy than on the other surfaces. Additionally the HREELS spectra of ethene on Pt(1 1 1) and the Pt-Sn surface alloys differ only slightly in terms of the energetic positions of the loss peaks.     

First-principles calculations on Al/AlB2 interfaces

The AlB₂ (1 1 1) surfaces and Al (1 1 1)/AlB₂ (0 0 0 1) interface were studied by first-principles calculations to clarify the heterogeneous nucleation potential of α-Al grains on AlB₂ particles in purity aluminium and hypoeutectic Al-Si alloys. It is demonstrated that the AlB₂ (0 0 0 1) surface models with more than nine atomic layers exhibit bulk-like interior, wherein the interlayer relaxations localized within the top three layers are well converged. The outmost layer of AlB₂ free surface having a preference of metal atom termination is evidenced by surface energy calculations. With Al atoms continuing the natural stacking sequence of bulk AlB₂, Al-Al metallic bonds are formed across interface during the combination of Al atoms with Al-terminated AlB₂ surface. The calculated interfacial energy of the Al/AlB₂ interface is much larger than that between the α-Al and aluminium melts, elucidating the poor nucleation potency of α-Al grains on AlB₂ particles from thermodynamic considerations.     

Study of interface interactions in B4C/Ni-Cr-Si system

Boron carbide is a ceramic material possessing unique properties, and hence, high technological applications. The wetting behavior of ceramics by liquid alloys, which is of crucial importance in a variety of materials processing technologies, is determined by interfacial chemical interactions. In the present paper, the interfacial interactions of B₄C with a series of Ni-Cr-Si alloys with Ni/Cr = 3.4 have been studied. For this purpose, a thermodynamic method was developed to predict the interactions. In addition, the interfacial structure and chemical composition were examined using SEM-EDS technique. Good agreement was found between the theoretical calculations and experimental data. It was revealed that the amount of Si content in the alloys plays a major role on the interfacial reactions as well as the interface microstructure.     

A theoretical investigation on Pt3Sn(1 0 2) surface alloy and CO-Pt3Sn(1 0 2) system

The adsorption properties of CO on experimentally verified stepped Pt₃Sn(1 0 2) surface were investigated using quantum mechanical calculations. The two possible terminations of Pt₃Sn(1 0 2) were generated and on these terminations all types of possible adsorption sites were determined. The adsorption energies and geometries of the CO molecule for all those sites were calculated. The most favorable sites for adsorption were determined as the short bridge site on the terrace of pure-Pt row of the mixed-atom-ending termination, atop site at the step-edge of the pure row of pure-Pt-ending termination and atop site at the step-edge of the pure-Pt row of the mixed-atom-ending termination. The results were compared with those for similar sites on the flat Pt₃Sn(1 1 0) surface considering the fact that Pt₃Sn(1 0 2) has terraces with (1 1 0) orientation. The LDOS analysis of bare sites clearly shows that there are significant differences between the electronic properties of Pt atoms at stepped Pt₃Sn(1 0 2) surface and the electronic properties of Pt atoms at flat (1 1 0) surface, which leads to changes in the CO bonding energies of these Pt atoms. Adsorption on Pt₃Sn(1 0 2) surface is in general stronger compared to that on Pt₃Sn(1 1 0) surface. The difference in adsorption strength of similar sites on these two surface terminations is a result of stepped structure of Pt₃Sn(1 0 2). The local density of states (LDOS) of the adsorbent Pt and C of adsorbed CO was utilized. The LDOS of the surface metal atoms with CO-adsorbed atop and of their bare state were compared to see the effect of CO chemisorption on the electron density distribution of the corresponding Pt atom. The downward shift in energy peak in the LDOS curves as well as changes in the electron densities of the corresponding energy levels indicate the orbital mixing between CO molecular orbitals and metal d-states. The present study showed that the adsorption strength of the sites has a direct relation with their LDOS profiles.     

A density functional theory study on the adsorption and dissociation of N2O on Cu2O(1 1 1) surface

Density functional theory has been employed to investigate the adsorption and the dissociation of an N₂O at different sites on perfect and defective Cu₂O(1 1 1) surfaces. The calculations are performed on periodic systems using slab model. The Lewis acid site, Cu_CUS, and Lewis base site, O_SUF are considered for adsorption. Adsorption energies and the energies of the dissociation reaction N₂O → N₂ + O(s) at different sites are calculated. The calculations show that adsorption of N₂O is more favorable on Cu_CUS adsorption site energetically. Cu_CUS site exhibits a very high activity. The Cu_CUS-N₂O reaction is exothermic with a reaction energy of 77.45 kJ mol⁻¹ and an activation energy of 88.82 kJ mol⁻¹, whereas the O_SUF-N₂O reaction is endothermic with a reaction energy of 205.21 kJ mol⁻¹ and an activation energy of 256.19 kJ mol⁻¹. The calculations for defective surface indicate that O vacancy cannot obviously improve the catalytic activity of Cu₂O.     

Adsorption properties of CO on low-index Pt3Sn surfaces

The adsorption properties of CO on Pt₃Sn were investigated by utilizing quantum mechanical calculations. The (1 1 1), (1 1 0) and (0 0 1) surfaces of Pt₃Sn were generated with all possible bulk terminations, and on these terminations all types of active sites were determined. The adsorption energies and the geometries of the CO molecule at those sites were found. Those results were compared with the results obtained from the adsorption of CO on similar sites of Pt(1 1 1), Pt(1 1 0) and Pt(0 0 1) surfaces. The comparison reveals that adsorption of CO is stronger on Pt surfaces; this may be the reason why catalysts with Pt₃Sn phase do not suffer from CO posioning in experimental works. Aiming to understand the interactions between CO and the metal adsorption sites in detail, the local density of states (LDOS) profiles were produced for atop-Pt adsorption, both for the carbon end of CO for its adsorbed and free states, and for the Pt atom of the binding site. LDOS profiles of C of free and adsorbed CO and Pt for corresponding pure Pt surfaces, Pt(1 1 1), Pt(1 1 0) and Pt(0 0 1) were also obtained. The comparison of the LDOS profiles of Pt atoms of atop adsorption sites on the same faces of bare Pt₃Sn and Pt surfaces showed the effect of alloying with Sn on the electronic properties of Pt atoms. Comparison of LDOS profiles of the C end of CO in its free and atop adsorbed states on Pt₃Sn and LDOS of Pt on bare and CO adsorbed Pt₃Sn surface were used to clear out the electronic changes occurred on CO and Pt upon adsorption. The study showed that (i) inclusion of a Sn atom at the adsorption site structure causes dramatic decrease in stability which limits the number of possible CO adsorption sites on Pt₃Sn surface, (ii) the presence of Sn causes angles different from 180° for M-C-O orientation, (iii) the presence of Sn in the neighborhood of Pt on which CO is adsorbed causes superposition of the 5σ/1π derived-state peaks at the carbon end of CO and changes in adsorption energy of CO, (iv) Sn present beneath the adsorption site strengthens the CO adsorption, whereas neighboring Sn on the surface weakens it for all Pt₃Sn surfaces tested and (v) the most stable site for CO adsorption is the atop-Pt site of the mixed atom termination of Pt₃Sn(1 1 0).     

Segregation of Pt at clean surfaces of (Pt, Ni)3Al

Experimental evidence for surface segregation of Pt at (1 1 1) surfaces of ternary (Pt, Ni)₃Al alloys is presented, based upon Auger electron spectroscopy, low energy ion scattering, and angle-resolved X-ray photoelectron spectroscopy. Density functional calculations in the dilute limit confirm that Pt segregation is energetically favored.     

Experimental determination of solid-liquid interfacial energy for solid Sn in the Sn-Mg system

The equilibrated grain boundary groove shapes for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid were directly observed annealing a sample at the eutectic temperature for about 5 days with a radial heat flow apparatus. The thermal conductivities of the solid phase, κ_S, and the liquid phase, κ_L, for the groove shapes were measured. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient, the solid-liquid interfacial energy and grain boundary energy for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid have been determined to be (7.35 ± 0.36) × 10⁻⁸ Km, (136.41 ± 13.64) × 10⁻³ J m⁻² and (230.95 ± 25.40) × 10⁻³ J m⁻², respectively.     

Oxidation kinetics of thin copper films and wetting behaviour of copper and Organic Solderability Preservatives (OSP) with lead-free solder

The oxide formation on thin copper films deposited on Si wafer was studied by XPS, SEM and Sequential Electrochemical Reduction Analysis SERA. The surfaces were oxidized in air with a reflow oven as used in electronic assembly at temperatures of 100 °C, 155 °C, 200 °C, 230 °C and 260 °C. The SERA analyses detected only the formation of Cu₂O but the XPS analysis done for the calibration of the SERA equipment proved also the presence of a CuO layer smaller than 2 nm above the Cu₂O oxide. The oxide growth follows a power-law dependence on time within this temperature range and an activation energy of 33.1 kJ/mol was obtained. The wettability of these surfaces was also determined by measuring the contact angle between solder and copper substrate after the soldering process. A correlation between oxide thickness and wetting angle was established. It was found that the wetting is acceptable only when the oxide thickness is smaller than 16 nm. An activation energy of 27 kJ/mol was acquired for the spreading of lead free solder on oxidized copper surfaces.From wetting tests on copper surfaces protected by Organic Solderability Preservatives (OSP), it was possible to calculate the activation energy for the thermal decomposition of these protective layers.     

Scaling behavior of island density in submonolayer growth of CaF2 on vicinal Si(1 1 1)

We have studied the scaling behavior of two-dimensional island density during submonolayer growth of CaF₂ on vicinal Si(1 1 1) surfaces using scanning tunneling microscopy. We have analyzed the morphology of the Si(1 1 1) surfaces where CaF₂ partial monolayers with coverages of about 0.1 monolayer are deposited at ∼600 °C. The number density of terrace nucleated islands increases with substrate terrace width l as ∼l⁴ in a low island density regime. This scaling behavior is consistent with predictions for the case of the irreversible growth of islands.     

Color centers in neutron-irradiated Y3Al5O12, CAF2 and LiF single crystals

The thermal annealing behavior of the Y₃Al₅O₁₂, CaF₂ and LiF single crystals bombarded at Algiers with reactor neutrons has been monitored by optical absorption spectroscopy. The irradiation was performed at about 315 K. On heating samples after irradiation, the optical absorption bands decrease and disappear completely at 873 and 523 K in the case of Y₃Al₅O₁₂ and CaF₂, respectively. Activation energies of 1.2±0.02 and 0.9±0.2 eV are estimated for Y₃Al₅O₁₂ and CaF₂, respectively. On the other hand, the LiF crystal shows a complex annealing behavior. Here, the optical absorption spectrum presents different shapes after each annealing temperature. Four steps are distinguished and discussed on heating samples from 300 to 673 K. Above 673 K, the absorption drops by about 50%; it completely disappears at 773 K.     

Eddy-current-resistant SmCo5/CaF2 magnets produced via high-energy milling in polar and non-polar liquids

Processes of high-energy ball milling of SmCo₅ alloys were compared for three single-liquid environments without using additional surfactants. Both coarsely grained as-cast and nanocrystalline pre-milled SmCo₅ precursors showed tendency toward formation of thin flakes if milled in polar liquids (acetone and ethanol) in a marked contrast to milling in non-polar heptane. CaF₂ dielectric powder added prior to milling in the polar liquids tends to become attached on the flake surfaces. Milling in heptane in the presence of CaF₂ produces flake-like SmCo₅ particles which with increasing the milling time are found to incorporate an increasing amount of CaF₂. The SmCo₅—5 wt% CaF₂ mixtures milled for the optimum time in both the polar and non-polar liquids were successfully hot-pressed into laminated composite magnets having intrinsic coercivity of 25–30 kOe, maximum energy product of approximately 6.5 MG Oe and electrical resistivity of 500–600 μΩ cm, which is more than 7 times the resistivity of conventional Sm–Co magnets.