Ripple-to-dome transition: the growth evolution of Ge on vicinal Si(1 1 10) surface

We present a detailed scanning tunnelling microscopy study which describes the morphological transition from ripple to dome islands during the growth of Ge on the vicinal Si(1 1 10) surface . Our experimental results show that the shape evolution of Ge islands on this surface is markedly different from that on the flat Si(001) substrate and is accomplished by agglomeration and coalescence of several ripples. By combining first principle calculations with continuum elasticity theory, we provide an accurate explanation of our experimental observations

Hug-like island growth of Ge on strained vicinal Si(111) surfaces

We examine the structure and the evolution of Ge islands epitaxially grown on vicinal Si(111) surfaces by scanning tunneling microscopy. Contrary to what is observed on the singular surface, three-dimensional Ge nanoislands form directly through the elastic relaxation of step-edge protrusions during the unstable step-flow growth. As the substrate misorientation is increased, the islands undergo a shape transformation which is driven by surface energy minimization and controlled by the miscut angle. Using finite element simulations, we show that the dynamics of islanding observed in the experiment results from the anisotropy of the strain relaxation.Comment: 4 figure

Step-step interaction on vicinal Si(001) surfaces studied by scanning tunneling microscopy

We report on measurements of step-step interaction on a flat Si(111)−(7×7) surface and on vicinal Si(001) surfaces with miscut angles ranging between 0.2° and 8°. Starting from scanning tunneling microscopy images of these surfaces and describing steps profile and interactions by the continuum step model, we measured the self-correlation function of single steps and the distribution of terrace widths. Empirical parameters, such as step stiffness and step-step interaction strength, were evaluated from the images. The present experiment allows to assess the dependence of the step-step repulsion on miscut angle, showing how parameters drawn from tunneling images can be used to interpolate between continuum mesoscopic models and atomistic calculations of vicinal surfaces

Islanding, growth mode and ordering in Si heteroepitaxy on Ge(001) substrates structured by thermal annealing

Si/Ge heteroepitaxial dots under tensile strain are grown on nanostructured Ge substrates produced by high-temperature flash heating exploiting the spontaneous faceting of the Ge(001) surface close to the onset of surface melting. A very diverse growth mode is obtained depending on the specific atomic structure and step density of nearby surface domains with different vicinal crystallographic orientations. On highly-miscut areas of the Ge(001) substrate, the critical thickness for islanding is lowered to about 5 ML, in contrast to the 11 ML reported for the flat Ge(001) surface, while on unreconstructed (1x1) domains the growth is Volmer-Weber driven. An explanation is proposed considering the diverse relative contributions of step and surface energies on misoriented substrates. In addition, we show that the bottom-up pattern of the substrate naturally formed by thermal annealing determines a spatial correlation for the dot sites

Mine clay washing residues as a source for alkali-activated binders

The aim of this paper is to promote the use of mine clay washing residues for the preparation of alkali activated materials (AAMs). In particular, the influence of the calcination temperature of the clayey by-product on the geopolymerization process was investigated in terms of chemical stability and durability in water. The halloysitic clay, a mining by-product, has been used after calcination and mixed with an alkaline solution to form alkali activated binders. Attention was focused on the influence of the clay’s calcination treatment (450–500–600◦C) on the geopolymers’ microstructure of samples, remaining in the lower limit indicated by the literature for kaolinite or illite calcination. The mixtures of clay and alkali activators (NaOH 8M and Na-silicate) were cured at room temperature for 28 days. The influence of solid to liquid ratio in the mix formulation was also tested in terms of chemical stability measuring the pH and the ionic conductivity of the eluate after 24-h immersion time in water. The results reported values of ionic conductivity higher for samples made with untreated clay or with low temperature of calcination (≥756 mS/m) compared with values of samples made with calcined clay (292 mS/m). This result suggests that without a proper calcination of the as-received clay it was not possible to obtain 25◦C-consolidated AAMs with good chemical stability and dense microstructure. The measures of integrity test, pH, and ionic conductivity in water confirmed that the best sample is made with calcined clay at 600◦C, being similar (53% higher ionic conductivity of the eluate) or equal (integrity test and pH) to values recorded for the metakaolin-based geopolymer considered the reference material. These results were reflected in term of reticulation and morphology of samples through the analysis with scanning electron microscope (SEM) and X-ray diffraction (XRD), which show a dense and homogeneous microstructure predominantly amorphous with minor amounts of quartz, halloysite, and illite crystalline phases. Special attention was dedicated to this by-product to promote its use, given that kaolinite (and metakaolin), as primary mineral product, has a strong impact on the environment. The results obtained led us to consider this halloysite clay very interesting as an aluminosilicate precursor, and extensively deepening its properties and reactivity for the alkaline activation. In fact, the heart of this work is to study the possibility of reusing this by-product of an industrial process to obtain more sustainable high-performance binders

Foundry sand alkali activation for sustainable construction

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Early stage of CVD graphene synthesis on Ge(001) substrate

In this work we shed light on the early stage of the chemical vapor deposition of graphene on Ge(001) surfaces. By a combined use of microRaman and x-ray photoelectron spectroscopies, and scanning tunneling microscopy and spectroscopy, we were able to individuate a carbon precursor phase to graphene nucleation which coexists with small graphene domains. This precursor phase is made of C aggregates with different size, shape and local ordering which are not fully sp2 hybridized. In some atomic size regions these aggregates show a linear arrangement of atoms as well as the first signature of the hexagonal structure of graphene. The carbon precursor phase evolves in graphene domains through an ordering process, associated to a re-arrangement of the Ge surface morphology. This surface structuring represents the embryo stage of the hills-and-valleys faceting featured by the Ge(001) surface for longer deposition times, when the graphene domains coalesce to form a single layer graphene film

Abrupt changes in the graphene on Ge(001) system at the onset of surface melting

By combining scanning probe microscopy with Raman and x-ray photoelectron spectroscopies, we investigate the evolution of CVD-grown graphene/Ge(001) as a function of the deposition temperature in close proximity to the Ge melting point, highlighting an abrupt change of the graphene's quality, morphology, electronic properties and growth mode at 930 degrees. We attribute this discontinuity to the incomplete surface melting of the Ge substrate and show how incomplete melting explains a variety of diverse and long-debated peculiar features of the graphene/Ge(001), including the characteristic nanostructuring of the Ge substrate induced by graphene overgrowth. We find that the quasi-liquid Ge layer formed close to 930 degrees is fundamental to obtain high-quality graphene, while a temperature decrease of 10 degrees already results in a wrinkled and defective graphene film.Comment: in pres

Driving with temperature the synthesis of graphene films on Ge(110)

We systematically investigate the chemical vapor deposition growth of graphene on Ge(110) as a function of the deposition temperature close to the Ge melting point. By merging spectroscopic and morphological information, we find that the quality of graphene films depends critically on the growth temperature improving significantly by increasing this temperature in the 910-930 {\deg}C range. We correlate the abrupt improvement of the graphene quality to the formation of a quasi-liquid Ge surface occurring in the same temperature range, which determines increased atom diffusivity and sublimation rate. Being observed for diverse Ge orientations, this process is of general relevance for graphene synthesis on Ge

Dynamical evolution of Ge quantum dots on Si(111): from island formation to high temperature decay

Heteroepitaxial growth is a process of profound fundamental importance as well as an avenue to realize nanostructures such as Ge/Si quantum dots (QDs), with appealing properties for applications in opto- and nanoelectronics. However, controlling the Ge/Si QD size, shape, and composition remains a major obstacle to their practical implementation. Here, Ge nanostructures on Si(111) were investigated in situ and in real-time by low energy electron microscopy (LEEM), enabling the observation of the transition from wetting layer formation to 3D island growth and decay. The island size, shape, and distribution depend strongly on the growth temperature. As the deposition temperature increases, the islands become larger and sparser, consistent with Brownian nucleation and capture dynamics. At 550 degrees C, two distinct Ge/Si nanostructures are formed with bright and dark appearances that correspond to flat, atoll-like and tall, faceted islands, respectively. During annealing, the faceted islands increase in size at the expense of the flat ones, indicating that the faceted islands are thermodynamically more stable. In contrast, triangular islands with uniform morphology are obtained from deposition at 600 degrees C, suggesting that the growth more closely follows the ideal shape. During annealing, the islands formed at 600 degrees C initially show no change in morphology and size and then rupture simultaneously, signaling a homogeneous chemical potential of the islands. These observations reveal the role of dynamics and energetics in the evolution of Ge/Si QDs, which can serve as a step towards the precise control over the Ge nanostructure size, shape, composition, and distribution on Si(111)