Phase transformation of Ni-B, Ni-P diffusion barrier deposited electrolessly on Cu interconnect

In this paper, we report that the phase transformation of Ni-B, Ni-P diffusion barriers deposited electrolessly on Cu, for the reason that the Ni-P layer is a more effective diffusion barrier than the Ni-B layer. The Ni₃B crystallized was decomposed to Ni and B₂O₃ above 400 °C and the Ni₃P crystallized was decomposed to Ni and P₂O₅ above 600 °C respectively in Ar atmosphere. Also, the Ni₃B was decomposed to Ni and free B above 400 °C and the Ni₃P was decomposed to Ni and free P above 600 °C respectively in H₂ atmosphere. The decomposed Ni formed a solid solution with Cu. The Cu diffusion occurred above 400 °C for Ni-B layer and above 600 °C for Ni-P layer, respectively. Because the decomposition temperature of Ni-P layer is about 200 °C higher than that of Ni-B layer, the Ni-P layer is a more effective barrier for Cu than the Ni-B layer.     

Hydrogen adsorption on GaAs(0 0 1)-c(4 × 4)

Exposure of the As-terminated GaAs(0 0 1)-c(4 × 4) reconstructed surface to atomic hydrogen (H) at different substrate temperatures (50-480 °C) has been studied by reflection high-energy electron diffraction (RHEED) and scanning tunnelling microscopy (STM). Hydrogen exposure at low temperatures (∼50 °C) produces a disordered (1 × 1) surface covered with AsH_x clusters. At higher temperatures (150-400 °C) exposure to hydrogen leads to the formation of mixed c(2 × 2) and c(4 × 2) surface domains with H adsorbed on surface Ga atoms that are exposed due to the H induced loss of As from the surface. At the highest temperature (480 °C) a disordered (2 × 4) reconstruction is formed due to thermal desorption of As from the surface. The results are consistent with the loss of As from the surface, either through direct thermal desorption or as a result of the desorption of volatile compounds which form after reaction with H.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.     

Formation of 10-30 nm SiO2/Si structure with a uniform thickness at ∼120 °C by nitric acid oxidation method

Silicon dioxide (SiO₂) layers with a thickness more than 10 nm can be formed at ∼120 °C by direct Si oxidation with nitric acid (HNO₃). Si is initially immersed in 40 wt.% HNO₃ at the boiling temperature of 108 °C, which forms a ∼1 nm SiO₂ layer, and the immersion is continued after reaching the azeotropic point (i.e., 68 wt.% HNO₃ at 121 °C), resulting in an increase in the SiO₂ thickness. The nitric acid oxidation rates are the same for (1 1 1) and (1 0 0) orientations, and n-type and p-type Si wafers. The oxidation rate is constant at least up to 15 nm SiO₂ thickness (i.e., 1.5 nm/h for single crystalline Si and 3.4 nm/h for polycrystalline Si (poly-Si)), indicating that the interfacial reaction is the rate-determining step. SiO₂ layers with a uniform thickness are formed even on a rough surface of poly-Si thin film.     

Microstructural evolution upon annealing in Ar-implanted Si

The annealing effects of crystalline silicon (Si) implanted with argon (Ar) ions at a dose of 2 × 10¹⁶ Ar⁺/cm² at room temperature and subsequently annealed at 400-1100 °C for 30 min were investigated. The samples were analyzed by transmission electron microscopy and Raman spectroscopy. Before and after annealing up to 600 °C, an amorphous layer is formed but Ar bubbles are not observed in the damage layer. After annealing at 800 °C, argon bubbles are observed together with extended defects. The damage layer evolves into a polycrystalline structure. After annealing at 1100 °C; exfoliation occurs on the sample surface, and microtwin lamellas form in the damage layer. Raman scattering revealed that a strong recrystallization occurs from 600 °C to 800 °C. The results were compared with the case of helium implantation, with particular focus on bubble formation mechanisms.     

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.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.     

Spectroscopic characterization of Ni films on sub-10-nm silica layers: Thermal metamorphosis and chemical bonding

The thermal evolution in the chemical and physical characteristics of the Ni film of thickness 1-50 nm deposited on silica of thickness less than 10 nm was studied. The chemical composition of silica affected the thermal behavior of the Ni overlayer substantially. Nickel deposited on native oxide may diffuse downward into native oxide during annealing and was oxidized. It mainly produced Ni₃O₂ and silicides below 150 °C. Increasing the temperature to 300 °C caused further oxidation of Ni to yield NiO. The sub-10-nm silicon dioxide layer, on the other hand, can inhibit the diffusion of Ni atoms downward when the Ni-deposited sample was annealed. Instead, these atoms aggregated into small particles on the surface at elevated temperatures, causing the substrate to be exposed. The size of the particles produced can be controlled, as it increased almost linearly with the thickness of the Ni film deposited in the low thickness regime. The thinner Ni films yielded smaller, round nanoparticles with better dispersity. The particles formed were strongly adhered to the silicon dioxide surface. The bulk of the particles formed was mainly metallic. Exposing to the air of the Ni particles formed on silicon dioxide mainly produces Ni₂O₃ on the particles.     

Magnetic properties and microstructure of x/FePt (x=Ge,GePt) bilayer

We have investigated the effect of Ge, GePt underlayers on the formation of ordered L1₀ FePt films. With Ge underlayer, the Ge₃Pt₂ compound was formed during post-annealing at 400 °C for 1 h. Interlayer diffusion of Ge and FePt layer suppress the formation of ordered L1₀ FePt phase. With Ge₂Pt₃ underlayer, the FePt film was ordered at 350 °C and the in-plane coercivity was 5.1 kOe. The ordering temperature was reduced to about 50 °C compared to the single-layer FePt film.     

Formation of Ge islands from a Ge layer on Si substrate during post-growth annealing

We have deposited a 12 nm thick Ge layer on Si(1 0 0) held at 200 °C by thermal evaporation under high vacuum conditions. Upon subsequent thermal annealing in vacuum, self-assembled growth of nanostructural Ge islands on the Ge layer occurred. Atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS) were used to characterize such layers. GISAXS measurements evidenced the formation of cylinder shaped structures upon annealing at 700 °C, which was confirmed by AFM measurements with a very sharp tip. A Ge mass transport from the layer to the islands was inferred by X-ray reflectivity and an activation energy of 0.40 ± 0.10 eV for such a process was calculated.     

Evolution of Si0.8Ge0.2 quantum dots during Si encapsulation

Surface structure, determined by scanning tunneling microscopy (STM), surface morphology, determined by atomic force microscopy (AFM), and surface composition, determined by X-ray photoelectron spectroscopy (XPS) of 20.0 nm Si_0.8Ge_0.2 quantum dots formed at 800 °C and encapsulated with 0-10 nm of Si at 500 °C and 800 °C are presented. It is observed that the quantum dot surface morphology changes during the Si encapsulation at 800 °C by the smoothing of the quantum dots. The height of the quantum dots decreases faster than can be accounted for from the amount of Si deposited, indicating that there is movement of material out of the quantum dots during the encapsulation process. Encapsulation at 500 °C results in a retention of the quantum dot surface morphology with increased Ge segregation compared to Si encapsulation at 800 °C. We conclude that the changing surface morphology at 800 °C is not the result of Ge segregation but due to intermixing resulting from the tensile strain of Si depositing on SiGe.     

Crystallization and surface morphology of Au/SiO2 thin films following furnace and flame annealing

A crystallization and surface evolution study of Au thin film on SiO₂ substrates following annealing at different temperatures above the eutectic point of the Au/Si system are reported. Samples were prepared by conventional evaporation of gold in a high vacuum (10⁻⁷ mbar) environment on substrates at room temperature. Thermal treatments were performed by both furnace and flame annealing techniques. Au thin films can be crystallized on SiO₂ substrates by both furnace and flame annealing. Annealing arranges the Au crystallites in the (1 1 1) plane direction and changes the morphology of the surface. Both, slow and rapid annealing result in a good background in the XRD spectra and hence clean and complete crystallization which depends more on the temperature than on the time of annealing. The epitaxial temperature for the Au/SiO₂ system decreases in the range of 350-400 °C. Furnace and flame annealing also form crystallized gold islands over the Au/SiO₂ surface. Relaxation at high temperatures of the strained Au layer, obtained after deposition, should be responsible for the initial stages of clusters formation. Gold nucleation sites may be formed at disordered points on the surface and they become islands when the temperature and time of annealing are increased. The growth rate of crystallites is highest around 360 °C. Above this temperature, the layer melts and gold diffuses from the substrate to the nucleation sites to increase the distance between islands and modify their shapes. Well above the eutectic temperature, the relaxed islands have hexagonally shaped borders. The mean crystallite diameters grow up to a maximum mean size of around 90 nm. The free activation energy for grain boundary migration above 360 °C is 0.2 eV. Therefore the type of the silicon substrate changes the mechanism of diffusion and growth of crystallites during annealing of the Au/Si system. Epitaxial Au(1 1 1) layers without formation of islands can be prepared by furnace annealing in the range of 300-310 °C and by flame annealing of a few seconds and up to 0.5 min.     

Effect of buffer layer on VOx film fabrication by reactive RF sputtering

Vanadium oxide VO_x films were fabricated by RF magnetron sputtering on various metal buffer layers or silica glass substrates at a substrate temperature of 400 °C. V₂O₅ film was fabricated on a silica glass substrate, and VO₂ films were fabricated on V, W, Fe, Ni, Ti, and Pt metal buffer layers. The transition temperature of the sample on the V buffer layer was 68 °C and that on the W buffer layer was 53 °C. The VO₂ film was also fabricated on the V buffer layer by non-reactive sputtering using a V₂O₅ target at a substrate temperature of 400 °C.     

XPS study of annealing induced effects on surface and interface electronic properties of Si/Ge nanostructures

The present study is focused on the influence of vacuum thermal treatment on surface/interface electronic properties of Si/Ge multilayer structures (MLS) characterized using X-ray photoelectron spectroscopy (XPS) technique. Desired [Si(5 nm)/Ge(5 nm)]_×10 MLS were prepared using electron beam evaporation technique under ultra high vacuum (UHV) conditions. The core-level XPS spectra of as-deposited as well as multilayer samples annealed at different temperatures such as 100 °C, 150 °C and 200 °C for 1 h show substantial reduction in Ge 2p peak integrated intensity, whereas peak intensity of Si 2p remains almost constant. The complete interdiffusion took place after annealing the sample at 200 °C for 5 h as confirmed from depth profiling of annealed MLS. The asymmetric behaviour in intensity patterns of Si and Ge with annealing was attributed to faster interdiffusion of Si into Ge layer. However, another set of experiments on these MLS annealed at 500 °C suggests that interdiffusion can also be studied by annealing the system at higher temperature for relatively shorter time duration.     

In-situ study of the catalytic oxidation of CO on a Pt(1 1 0) surface using ambient pressure X-ray photoelectron spectroscopy

CO and O₂ co-adsorption and the catalytic oxidation of CO on a Pt(1 1 0) surface under various pressures of CO and O₂ (up to 250 mTorr) are studied using ambient pressure X-ray photoelectron spectroscopy (APXPS) and mass spectrometry. There is no surface oxide formation on Pt under our reaction conditions. CO oxidation in this pressure (<500 mTorr), O₂ to CO ratio (<10), and temperature (150 °C) regime is consistent with the Langmuir-Hinshelwood reaction mechanism. Our findings provide in-situ surface chemical composition data of the catalytic oxidation of CO on Pt(1 1 0) at total pressures below 1 Torr.     

Double layer oxidation resistant coating for carbon fiber reinforced silicon carbide matrix composites

Double layer coatings, with celsian-Y₂SiO₅ as inner layer and Y₂Si₂O₇ as outer layer, were prepared by microwave sintering on the surface of carbon fiber reinforced silicon carbide matrix composite. Both celsian, Y₂SiO₅ and Y₂Si₂O₇ were synthesized by in situ method using BAS glass, Y₂O₃ and SiO₂ as staring materials. The sintering temperature was 1500 °C, and little damage was induced to the composite. The composition and micrograph of the fired coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The oxidation and thermal shock resistance of samples with doubled-layered coating were characterized at 1400 °C in air. After 150 min oxidation and thermal cycling between 1400 °C and room temperature for 15 times, the weight loss of double layer-coated sample was 1.22% and there were no cracks in the coating.     

Annealing and measurement temperature dependence of W2B5-based rectifying contacts to n-GaN

The thermal stability and measurement temperature dependence of Schottky contact characteristics on n-GaN using a W₂B₅/Ti/Au metallization scheme was studied using current-voltage (I-V), scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) measurements. The elemental profile obtained from samples annealed at 350 °C showed some titanium diffusion into the gold layer but little other difference from the as-deposited wafer. Annealing at 700 °C produced significant diffusion of titanium. The Schottky barrier height increased with anneal temperature up to 200 °C, reaching a maximum value of 0.65 eV, but decreased at higher annealing temperatures. The reverse breakdown voltage from diodes fabricated using the W₂B₅-based contacts showed a similar dependence. The reverse current magnitude was larger than predicted by thermionic emission alone. The barrier height showed only minor changes with measurement temperature up to 150 °C.     

Decay of multilayer holes on SrTiO3(0 0 1)

We have studied the decay kinetics of nanoscale multilayer holes on SrTiO₃(0 0 1) surfaces, using variable temperature scanning tunneling microscopy. We have performed real time observation of the decay of multilayer holes with diameters of 10 nm order at 750 °C. We have found that the hole decays, filling layer by layer from the bottom while expanding the periphery of the hole. We have performed numerical simulations of hole decay based on a step flow model. The observed decay kinetics is found to be diffusion limited with local mass conservation.     

Thickness dependence on thermal stability of sputtered Ag nanolayer on Ti/Si(1 0 0)

Thermal stability of Ag layer on Ti coated Si substrate for different thicknesses of the Ag layer have been studied. To do this, after sputter-deposition of a 10 nm Ti buffer layer on the Si(1 0 0) substrate, an Ag layer with different thicknesses (150-5 nm) was sputtered on the buffer layer. Post annealing process of the samples was performed in an N₂ ambient at a flow rate of 200 ml/min in a temperature range from 500 to 700 °C for 30 min. The electrical property of the heat-treated multilayer with the different thicknesses of Ag layer was examined by four-point-probe sheet resistance measurement at the room temperature. Phase formation and crystallographic orientation of the silver layers were studied by θ-2θ X-ray diffraction analysis. The surface topography and morphology of the heat-treated films were determined by atomic force microscopy, and also, scanning electron microscopy. Four-point- probe electrical measurement showed no considerable variation of sheet resistance by reducing the thickness of the annealed Ag films down to 25 nm. Surface roughness of the Ag films with (1 1 1) preferred crystallographic orientation was much smaller than the film thickness, which is a necessary condition for nanometric contact layers. Therefore, we have shown that the Ag layers with suitable nano-thicknesses sputtered on 10 nm Ti buffer layer were thermally stable up to 700 °C.     

Improvement of corrosion resistance of nitrided low alloy steel by plasma post-oxidation

Post-oxidizing treatments can be performed to improve the corrosion resistance of nitrided steel samples. In this paper, plasma nitriding treatments were performed at 540 °C for 4 h using ammonia as the working gas, and plasma post-oxidizing treatments were carried out at temperatures ranging from 350 °C to 500 °C for 2 h in oxygen gas. The treated samples were characterized by using optical microscopy, SEM, XRD, and electrochemical polarization. The X-ray analysis revealed the formation of iron-nitride phases of ?-Fe_2-3N and γ′-Fe₄N during plasma nitriding and iron oxide phases of hematite (Fe₂O₃) and magnetite (Fe₃O₄) through the post-oxidizing treatment. In particular, it was found that the very thin magnetite layer 0.8-1.5 μm in thickness on top of the compound layer was obtained by plasma post-oxidized at 400 °C and 450 °C. It was also demonstrated that the corrosion characteristics of the nitrided compound layer were further improved by post-oxidation treatment.