Effects of deposition temperature and thickness on the structural properties of thermal evaporated bismuth thin films

Bismuth (Bi) thin films of different thicknesses were deposited onto Si(1 0 0) substrate at various substrate temperatures by thermal evaporation technique. Influences of thickness and deposition temperature on the film morphologies, microstructure, and topographies were investigated. A columnar growth of hexahedron-like grains with bimodal particle size distribution was observed at high deposition temperature. The columnar growth and the presence of large grains induce the Bi films to have large surface roughness as evidenced by atomic force microscopy (AFM). The dependence of the crystalline orientation on the substrate temperature was analyzed by X-ray diffraction (XRD), which shows that the Bi films have completely randomly oriented polycrystalline structure with a rhombohedral phase at high deposition temperature (200 °C) and were strongly textured with preferred orientation at low deposition temperatures (30 and 100 °C).     

Ag induced restructuring of the oxygen precovered Cu(1 1 0) surface

The interplay between chemisorbed oxygen and deposited Ag on the Cu(1 1 0) surface has been studied by scanning tunneling microscopy (STM) and photoelectron emission microscopy (PEEM). The Cu-CuO stripe phase formed on the clean Cu(1 1 0) surface upon oxygen chemisorption at 660 K is partly dissolved by Ag deposition at 300 K. Upon annealing, however, a phase separation is observed, where the Cu-O compounds agglomerate into large CuO islands and the Ag is located in between. Also a strong preference for the Ag to attach to step bunches is observed. Especially on the fully (2×1)O reconstructed Cu(1 1 0) surface, all the deposited Ag is found at the step bunches giving rise to a contrast in PEEM.     

Morphological evidence for surface pre-melting on Si(1 1 1)

We present what we believe to be the first morphological evidence for the occurrence of surface pre-melting on the Si(1 1 1) surface. Our results complement the extensive previous evidence from diffraction and ion scattering techniques for the presence of pre-melted (liquid-like) layers on Si(1 1 1) below the bulk melting temperature and also suggest how atomic steps are involved in the initiation of such layers. Our results are based on atomic force microscopy studies of morphologies that are preserved when surfaces are annealed in a range of high temperatures and then rapidly cooled to room temperature for observation. A unique feature of the experiments is the use of specially prepared atomically flat or very low step density surfaces; this allows us to see how the liquid-like morphologies are associated with the steps and also allows the high temperature structures to survive the cooling process without being absorbed into the steps which normally would exist on a surface vicinal to (1 1 1). Quenched-in structures ascribed to pre-melting also act as sinks for diffusing ‘excess’ adatoms generated by the (1 × 1) to (7 × 7) transition and this leads to the formation of dendritic islands.     

Spatio-temporal dynamics of the NO + NH3 reaction on polycrystalline platinum

Spontaneous reaction rate oscillations and spatio-temporal patterns have been observed by mass spectrometry and photoemission electron microscopy (PEEM) during the reduction of NO by NH₃ on polycrystalline platinum at 1 × 10⁻⁴ Torr and temperatures from 460-520 K. The appearance of both oscillations and patterns was found to be strongly dependent on the gas phase composition and the temperature. In addition, the overall dynamics of the catalyst were found to be dominated by the nonlinear behavior of Pt(1 0 0) type grains, while other types of grains did not participate. In contrast to previous studies, a large number of complex multimodal oscillations were observed, particularly as the coupling between the surface and the gas phase was increased. The appearance of these complex oscillations demonstrates the importance of gas phase coupling to understanding catalytic reactions, even in high vacuum systems.     

Sub-Angstrom oscillation amplitude non-contact atomic force microscopy for lateral force gradient measurement

We report the first results from novel sub-Angstrom oscillation amplitude non-contact atomic force microscopy developed for lateral force gradient measurements. Quantitative lateral force gradients between a tungsten tip and Si(1 1 1)-(7 × 7) surface can be measured using this microscope. Simultaneous lateral force gradient and scanning tunnelling microscope images of single and multi atomic steps are obtained. In our measurement, tunnel current is used as feedback. The lateral stiffness contrast has been observed to be 2.5 N/m at single atomic step, in contrast to 13 N/m at multi atomic step on Si(1 1 1) surface. We also carried out a series of lateral stiffness-distance spectroscopy. We observed lateral stiffness-distance curves exhibit sharp increase in the stiffness as the sample is approached towards the surface. We usually observed positive stiffness and sometimes going into slightly negative region.     

A comparative STM study of Ru nanoparticles deposited on HOPG by mass-selected gas aggregation versus thermal evaporation

Scanning tunneling microscopy was used to compare the morphologies of Ru nanoparticles deposited onto highly-oriented graphite surfaces using two different physical vapour deposition methods; (1) pre-formed mass-selected Ru nanoparticles with diameters between 2 nm and 15 nm were soft-landed onto HOPG surfaces using a gas-aggregation source and (2) nanoparticles were formed by e-beam evaporation of Ru films onto HOPG. The particles generated by the gas-aggregation source are round in shape with evidence of facets resolved on the larger particles. Annealing these nanoparticles when they are supported on unsputtered HOPG resulted in the sintering of smaller nanoparticles, while larger particles remained immobile. Nanoparticles deposited onto sputtered HOPG surfaces were found to be stable against sintering when annealed. The size and shape of nanoparticles deposited by e-beam evaporation depend to a large extent on the state of the graphite support and the temperature. Ru deposition onto unsputtered HOPG is characterised by bimodal growth with large flat particles formed on the substrate terraces and smaller diameter particles aligned along the substrate steps. Evaporation onto sputtered HOPG results in the formation of 2 nm round particles with a narrow size distribution. Finally, thermal deposition onto both sputtered and unsputtered HOPG at 660 °C results in larger particles showing a flat Ru(0 0 0 1) top facet.     

Morphologies of solid-liquid interface and surface steps during rapid growth of BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> single crystals

The evolution of solid-liquid interface during BBO single crystal growth was studied by the differential interference microscopy. And the step morphology on (0001) surface of the as-grown crystal was observed by the atomic force microscopy as well. It was found that the transition from a flat solid-liquid interface to a skeletal shape will occur in case of rapid growth. However, AFM images of surface steps revealed morphology differences correlated with crystallographic directions. The steps advancing along 〈10 0〉 direction form the step flow, whereas those steps propagating along 〈01 0〉 direction shape into step segments. Measurements of step heights by AFM indicated that it is the high anisotropy of the dimension of growth unit and step bunching due to the enlargement of concentration difference along the surface that results in the anisotropy of step morphologies. Supported by the National Natural Science Foundation of China (Grant No. 50331040) and the Innovation Funds from Shanghai Institute of Ceramics, Chinese Academy of Sciences (Grant No. SCX0623)     

X-ray topography of polydiacetylene single crystals prepared by using physical vapor growth technique

The lattice defects in polydiacetylene (PDA) single crystals prepared using physical vapor growth were investigated by white beam X-ray topography. Line patterns along the [0 0 1] and [1 0 2] directions were clearly observed. Appearance of the line patterns along the [0 0 1] direction proves the polymerization direction predicted by Hädicke et al. The topographic results are in good agreement with the surface morphologies investigated by atomic force microscopy (AFM).     

Novel synthesis and electrophoretic response of low density TiO-TiO2-carbon black composite

Novel low density TiO-TiO₂-carbon black composite was synthesized, which involved the deposition of inorganic coating on the surface of core-shell latex particles and subsequent removal of latex particles by calcination in high-purity nitrogen. The morphology and interior structure were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The images exhibited the composite had spherical shape and smooth surface, and the interior structure was hollow or porous. X-ray diffraction peaks (XRD) were mostly in agreement with the standard diffraction patterns of rutile TiO₂. In addition, the observed peaks at 2θ of 43.5°, 50.6° and 74.4° can be indexed to (1 1 1), (2 0 0) and (2 2 0) planes of cubic phase TiO. The X-ray photoelectron spectroscopy (XPS) results indicated that composite consisted of carbon black, TiO and TiO₂. The apparent density of the composite was suitable to 1.62 g cm⁻³, due to density matching with suspending media. Glutin-arabic gum microcapsules containing TiO-TiO₂-carbon black composite electrophoretic liquid were prepared via complex coacervation. The particles in the microcapsules showed excellent electrophoretic mobility under a DC field.     

Hillock sizes after wet etching in silicon

The formation of two- and three-dimensional hillocks is regularly observed in Si(1 1 1) steps and Si(1 0 0) during wet etching. Frequently the resulting morphology consists of hillocks scattered on a landscape of limited roughness. Recently we proposed a mean field model (MFM) in which the observed hillock-and-valley pattern is possible under steady state if hillock etching is slightly faster than valley etching. This condition implies that hillock size distributions must be an exponential decreasing function. In this work, we report a systematic study of hillock size distributions of experimental morphologies obtained under different etchant concentrations in Si(1 0 0). We found that experimental hillock size distributions are in agreement with those predicted by the MFM.     

Observation of triangle pits in PbSe grown by molecular beam epitaxy

PbSe thin films on BaF₂ (1 1 1) were grown by molecular beam epitaxy with different selenium beam flux. Evolution of PbSe surface morphologies with Se/PbSe beam flux ratio (R_f) has been studied by atomic force microscopy and high-resolution X-ray diffraction. Growth spirals with monolayer steps on PbSe surface are obtained using high beam flux ratio, R_f ≥ 0.6. As R_f decreases to 0.3, nano-scale triangle pits are formed on the surface and the surface of PbSe film changes to 3D islands when R_f = 0. Glide of threading dislocations in 〈1 1 0〉{1 0 0}-glide system and Pb-rich atom agglomerations are the formation mechanism of spiral steps and triangle pits. The nano-scale triangle pits formed on PbSe surface may render potential applications in nano technology.     

RHEED wave functions and the effect of reconstruction on secondary electron emission from the Si(1 0 0) surface

The effect of surface reconstruction on contrast in scanning electron microscopy of the Si(1 0 0)-2 × 1 surface is investigated. A theory of the initial secondary production rate is developed and an upper bound on the rate is shown to depend on the product of the integrated intensities of the initial and final RHEED states. These states are calculated with a reflection matrix method and their depth dependence is investigated. The results are used to analyse scanning electron microscopy contrast in images of 1 × 2- and 2 × 1-regions of the Si(1 0 0)-2 × 1 surface reported by Watanabe et al. The calculated integrated intensities are consistent with the experimental images and with the experimentally observed dependence of the contrast on the azimuth of the incident electron beam. This supports the idea that the observed contrast is caused by the effect of surface reconstruction on the RHEED states.     

Carbide induced reconstruction of monatomic steps on Ni(1 1 1) - A density functional study

We present density functional calculations for carbon adsorption at the two types of monatomic steps on a Ni(1 1 1) surface. We show that it is thermodynamically favourable to make a carbon induced clock-type reconstruction at the close-packed step with a [1 1 1] step geometry, which creates fourfold sites at the step-edge. It is furthermore possible to extend the carbide with the clock reconstructed geometry onto the upper terrace with a net energy gain compared to adsorption of carbon on unreconstructed close-packed steps or terrace sites on Ni(1 1 1). Our findings explain the fact that carbide islands start to grow preferentially on the close-packed steps as has been observed using scanning tunneling microscopy.     

Electrochemical Au deposition on stepped Si(1 1 1)-H surfaces: 3D versus 2D growth studied by AFM and X-ray diffraction

In order to grow magnetic layers on silicon substrates, a non-magnetic buffer layer is often needed to avoid silicide formation and to reproduce the perpendicular magnetic anisotropy obtained on metal single crystals, as in the case of Co on Au(1 1 1) and Pt(1 1 1). In this context, we have studied the electrochemical growth of Au buffer layers, and show that it is possible to obtain different film morphologies on hydrogen-terminated vicinal Si(1 1 1) surfaces by varying the electrochemical deposition parameters and solution composition. Two different morphologies have been obtained as observed by atomic force microscopy: continuous 2D Au films (chloride solution at pH 4), and films consisting in flat top 3D Au islands decorating the Si(1 1 1) step edges (cyanide solution at pH 14). X-ray diffraction measurements reveal that the gold layer and islands have Au(1 1 1) orientation and are in epitaxy with the Si(1 1 1) surface. In the case of islands, the lateral facets have also Au(1 1 1) orientation. Results are discussed within a model in which the breaking of the Si-H surface bonds plays a major role in the Au nucleation and growth mechanisms.     

Fabrication and scanning tunneling microscopy studies of the Si(1 1 1)-(√31 × √31)-In surface

We report on the fabrication of single phase of the Si(1 1 1)-(√31 × √31)-In reconstruction surface, observed by scanning tunneling microscopy (STM) at room temperature. By depositing specific amounts of indium atoms while heating the Si(1 1 1)-(7 × 7) substrate at a critical temperature, the single phase of Si(1 1 1)-(√31 × √31)-In surfaces could be routinely obtained over the whole surface with large domains. This procedure is certified by our high-resolution STM images in the range of 5-700 nm. Besides, the high resolution STM images of the Si(1 1 1)-(√31 × √31)-In surface were also presented.     

Texture change through film thickness and off-axis accommodation of (0 0 2) planes

We present our recent experimental results on the formation of off-axis texture and crystallographic tilting of crystallites that take place in thin film of transition metal nitrides. For this purpose, the microstructural development of TiAlN film was studied, specially the change in texture with film thickness. Fiber texture was measured using θ-2θ and pole figure X-ray diffraction (XRD), while scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the microstructure and changes in texture with thickness. The sin²ψ method was applied to determine the stresses on (1 1 1) and (0 0 2) plane. With deposition parameters chosen, the growth texture mechanism is discussed in three different stages of film growth. Surface energy minimization at low thickness leads to the development of (0 0 2) orientation. On the other hand, the competitive growth promotes the growth of (1 1 1) planes parallel to film surface at higher thickness. However, contrary to the prediction of growth models, the (0 0 2) grains are not completely overlapped by (1 1 1) grains at higher thickness. Rather the (0 0 2) grains still constitute the surface, but are tilted away from the substrate normal showing substantial in-plane alignment to allow the (1 1 1) planes remain parallel to film surface. Intrinsic stress along (1 1 1) and (0 0 2) shows a strong dependence with preferred orientation. The stress level in (0 0 2) grains which was compressive at low thickness changes to tensile at higher thickness. This change in the nature of stress allows the (0 0 2) planes to tilt away in order to promote the growth of 〈1 1 1〉 parallel to film normal and to minimize the overall energy of system due to high compressive stress stored in the (1 1 1) grains. The change in surface morphology with thickness was observed using SEM. An increase in surface roughness with film thickness was observed which indicates the development of (1 1 1) texture parallel to film surface. TEM observations support the XRD results regarding texture change. Film hardness was measured by nanoindentation and a correlation between (1 1 1) texture, stress and hardness is obtained. The results indicate that texture development is a complex interplay between thermodynamic and kinetic forces. An attempt is made to understand this phenomenon of off-axis accommodation of (0 0 2) at higher thicknesses, which is a new result not reported previously.     

TiAlN coatings deposited by triode magnetron sputtering varying the bias voltage

TiAlN films were deposited on AISI O1 tool steel using a triode magnetron sputtering system. The bias voltage effect on the composition, thickness, crystallography, microstructure, hardness and adhesion strength was investigated. The coatings thickness and elemental composition analyses were carried out using scanning electron microscopy (SEM) together with energy dispersive X-ray (EDS). The re-sputtering effect due to the high-energy ions bombardment on the film surface influenced the coatings thickness. The films crystallography was investigated using X-ray diffraction characterization. The X-ray diffraction (XRD) data show that TiAlN coatings were crystallized in the cubic NaCl B1 structure, with orientations in the {1 1 1}, {2 0 0} {2 2 0} and {3 1 1} crystallographic planes. The surface morphology (roughness and grain size) of TiAlN coatings was investigated by atomic force microscopy (AFM). By increasing the substrate bias voltage from −40 to −150 V, hardness decreased from 32 GPa to 19 GPa. Scratch tester was used for measuring the critical loads and for measuring the adhesion.     

Interaction of O2 with Pd single crystals in the range 1-150 Torr: Surface morphology transformations

The interaction of O₂ with Pd single crystals including Pd(1 1 1), Pd(1 1 0) and Pd(1 0 0) in the pressure range 1-150 Torr was studied using scanning tunneling microscopy (STM). The Pd single crystal surface morphologies were determined by the oxidation conditions: O₂ pressure, exposure time and treatment temperature. Oxygen dissolution into Pd metal followed by the formation of bulk oxide was observed. The dissolution of oxygen resulted in the increase of the inter-planar spacing between the first two layers, 9-14% increase after an exposure of Pd(1 1 1) to 10-25 Torr O₂ at 600 K for 10 min, and 10-20% increase after exposing Pd(1 1 0) and Pd(1 0 0) to 1 Torr O₂ at 600 K for 10 min. Elongated or semi-spherical oxide agglomerates along the steps nucleated and grew on both Pd(1 1 0) and Pd(1 0 0) surfaces after oxidation in 5-25 Torr O₂ at 600 K. When bulk PdO was formed, the single crystal surface was covered with semi-spherical agglomerates 2-4 nm in size, which tended to aggregate to form a “cauliflower-like” structure. The single crystal surface area also increased during oxidation.     

Sulfur-induced mobilization of Au surface atoms on Au(1 1 1) studied by real-time STM

The interaction of sulfur with gold surfaces has attracted considerable interest due to numerous technological applications such as the formation of self-assembled monolayers and as a chemical sensor. Here, we report on the interaction of sulfur with Au(1 1 1) at two different temperatures (300 K and 420 K) studied by real-time scanning tunnelling microscopy, low energy electron diffraction and Auger electron spectroscopy. In the low coverage regime (<0.1 ML), S adsorption lifts the herringbone reconstruction of the clean Au(1 1 1) surface indicating a lateral expansion of the surface layer. An ordered (√3 × √3)R30° sulfur adlayer develops as the coverage reaches ∼0.3 ML. At higher S coverages (>0.3 ML) gold surface atoms are removed from regular terrace sites and incorporated into a growing gold sulfide phase. At 300 K this process leads to the formation of a rough pit and mound surface morphology. This gold sulfide exhibits short-range order and an incommensurate, long-range ordered AuS phase develops upon annealing at 450-525 K. In contrast, formation of an ordered AuS phase via rapid step-retraction rather than etch pit formation is observed during S-interaction with Au(1 1 1) surfaces at 420 K. Our results shed new light on the S-Au(1 1 1) interaction.     

Observation of double- to single-domain transition on the Eu/Si(1 0 0) surface by LEED and STM

The orientational phase diagram and morphology of the Eu-adsorbed Si(1 0 0) surface miscut by 0.4° have been studied by low-energy electron diffraction and scanning tunneling microscopy. We demonstrate that the original double-domain configuration with single-layer steps on the Si(1 0 0) substrate can be drastically broken at 0.4 monolayer (ML) of Eu. At this coverage, the ordered domain pattern formed by topographically non-equivalent terraces with Eu-induced 2 × 3 and “2 × 1” (so-called “wavy” structure) reconstructions is found, while no orthogonal 3 × 2 and “1 × 2” domains are observed. A model of the single-domain surface is proposed. The origin of the double- to single-domain transition found for the Eu/Si(1 0 0) system is discussed.