Hints for a general understanding of the epitaxial rules for van der Waals epitaxy from Ge-Sb-Te alloys

In this study, a generalized guideline is identified to predict the interaction between two-dimensional (2D) layered materials and substrate surfaces. Additionally, the van der Waals (vdW) heterostructures commensurability, the phase formation and the strain relaxation are identified during interface growth. To achieve such a general overview, the case of Ge-Sb-Te (GST) alloys on InAs(111) is studied. In this system, low-lattice mismatch conditions are fulfilled to avoid relaxation due to formation of misfit dislocations and allow to correctly identify vdW epitaxy. At the same time, the substrate can be efficiently prepared into self- and un-passivated surfaces to clarify the role of the surface interaction. Furthermore, the GST epilayer exhibits two different highly ordered 2D structures and a three-dimensional disordered structure, allowing to directly infer the nature of the epitaxy. This study opens the way for the design and mastering of vdW epitaxial growth of 2D heterostructures as well as hybrid 2D and non-layered materials

Modulation of van der Waals and classical epitaxy induced by strain at the Si step edges in GeSbTe alloys

The present work displays a route to design strain gradients at the interface between substrate and van der Waals bonded materials. The latter are expected to grow decoupled from the substrates and fully relaxed and thus, by definition, incompatible with conventional strain engineering. By the usage of passivated vicinal surfaces we are able to insert strain at step edges of layered chalcogenides, as demonstrated by the tilt of the epilayer in the growth direction with respect of the substrate orientation. The interplay between classical and van der Waals epitaxy can be modulated with an accurate choice of the substrate miscut. High quality crystalline GexSb2Te3+x with almost Ge1Sb2Te4 composition and improved degree of ordering of the vacancy layers is thus obtained by epitaxial growth of layers on 3–4° stepped Si substrates. These results highlight that it is possible to build and control strain in van der Waals systems, therefore opening up new prospects for the functionalization of epilayers by directly employing vicinal substrates

Exchange current density as an effective descriptor of poisoning of active sites in platinum group metal-free electrocatalysts for oxygen reduction reaction

The oxygen reduction reaction (ORR) is of primary importance for the direct and clean conversion of energy in fuel cells, necessarily requiring an electrocatalyst to be exploited. At the state of the art, platinum group metal-free (PGM-free) electrocatalysts are the most promising alternative to carbon-supported Pt nanoparticles (Pt/C), which are more expensive and more performing but highly prone to deactivation in a contaminated working environment. The comparison of the two materials is at the level of fine-tuning, requiring specific activity descriptors, namely, turnover frequency (TOF) and site density (SD), to understand how to compare the performance of PGM-free electrocatalysts with Pt/C electrocatalysts. Specific probing molecules that bind with the active sites are required to evaluate the SD of PGM-free electrocatalysts. However, PGM-free electrocatalysts possess not a single active site like Pt/C, but a multitude of primary (metal-containing) and secondary (metal-free) sites arising from the pyrolysis synthesis process, eventually complicating SD evaluation. In this work, we propose a method for evaluating the direct interaction through the chemisorption of probing molecules over the PGM-free primary and secondary sites, the discrimination of which is of paramount importance in an effective SD evaluation. Based on the rotating disk electrode technique, the study investigates the electrochemistry of Fe-based PGM-free electrocatalysts poisoned with hydrogen sulfide at pH 1 in comparison with a Pt/C sample. In addition, X-ray photoelectron spectroscopy (XPS) is used to establish a relationship between the electrochemistry and surface chemistry of the poisoned material. The results identify the exchange current density as a meaningful tool that allows the discrimination of poisoning of specific active sites (metal-containing or metal-free). In addition, the understanding of the interaction phenomenon occurring between sites and probing molecules will be paramount for the selection of those contaminants capable of selectively interacting with the active sites of interest, paving the way to a more accurate SD evaluation

Structural and electrical properties of annealed Ge2Sb2Te5 films grown on flexible polyimide

The morphological, structural, and electrical properties of as-grown and annealed Ge2Sb2Te5 (GST) layers, deposited by RF-sputtering on flexible polyimide, were studied by means of optical microscopy, atomic force microscopy, X-ray diffraction, Raman spectroscopy, and electrical characterization. The X-ray diffraction annealing experiments showed the structural transformation of GST layers from the as-grown amorphous state into their crystalline cubic and trigonal phases. The onset of crystallization of the GST films was inferred at about 140 degrees C. The vibrational properties of the crystalline GST layers were investigated via Raman spectroscopy with mode assignment in agreement with previous works on GST films grown on rigid substrates. The electrical characterization revealed a good homogeneity of the amorphous and crystalline trigonal GST with an electrical resistance contrast of 8 x 10(6)

Complex domain wall dynamics in compressively strained GaMnAs epilayers

The domain wall induced reversal dynamics in compressively strained GaMnAs was studied employing the magneto-optical Kerr effect and Kerr microscopy. Due to the influence of an uniaxial part in the in-plane magnetic anisotropy (90+/-Delta) domain walls with considerably different dynamic behavior are observed. While the (90+Delta) reversal is identified to be propagation dominated with a small number of domain walls, the case of (90-Delta) reversal includes the nucleation of many domain walls. The domain wall nucleation/propagation energy for both transitions are estimated using model calculations from which we conclude that single domain devices can be achievable using the (90+Delta) mode.Comment: 4 figure

Thick Does the Trick: Genesis of Ferroelectricity in 2D GeTe-Rich (GeTe)m (Sb2 Te3 )n Lamellae

The possibility to engineer (GeTe)(m)(Sb2Te3)n phase-change materials to co-host ferroelectricity is extremely attractive. The combination of these functionalities holds great technological impact, potentially enabling the design of novel multifunctional devices. Here an experimental and theoretical study of epitaxial (GeTe)(m)(Sb2Te3)n with GeTe-rich composition is presented. These layered films feature a tunable distribution of (GeTe)m(Sb2Te3)(1) blocks of different sizes. Breakthrough evidence of ferroelectric displacement in thick (GeTe)m(Sb2Te3)(1) lamellae is provided. The density functional theory calculations suggest the formation of a tilted (GeTe)m slab sandwiched in GeTe-rich blocks. That is, the net ferroelectric polarization is confined almost in-plane, representing an unprecedented case between 2D and bulk ferroelectric materials. The ferroelectric behavior is confirmed by piezoresponse force microscopy and electroresistive measurements. The resilience of the quasi van der Waals character of the films, regardless of their composition, is also demonstrated. Hence, the material developed hereby gathers in a unique 2D platform the phase-change and ferroelectric switching properties, paving the way for the conception of innovative device architectures

Interface formation during the growth of phase change material heterostructures based on Ge-Rich Ge-Sb-Te alloys

In this study, we present a full characterization of the electronic properties of phase change material (PCM) double-layered heterostructures deposited on silicon substrates. Thin films of amorphous Ge-rich Ge-Sb-Te (GGST) alloys were grown by physical vapor deposition on Sb2Te3 and on Ge2Sb2Te5 layers. The two heterostructures were characterized in situ by X-ray and ultraviolet photoemission spectroscopies (XPS and UPS) during the formation of the interface between the first and the second layer (top GGST film). The evolution of the composition across the heterostructure interface and information on interdiffusion were obtained. We found that, for both cases, the final composition of the GGST layer was close to Ge2SbTe2 (GST212), which is a thermodynamically favorable off-stoichiometry GeSbTe alloy in the Sb-GeTe pseudobinary of the ternary phase diagram. Density functional theory calculations allowed us to calculate the density of states for the valence band of the amorphous phase of GST212, which was in good agreement with the experimental valence bands measured in situ by UPS. The same heterostructures were characterized by X-ray diffraction as a function of the annealing temperature. Differences in the crystallization process are discussed on the basis of the photoemission results

Growth, electronic and electrical characterization of Ge-Rich Ge-Sb-Te alloy

In this study, we deposit a Ge-rich Ge-Sb-Te alloy by physical vapor deposition (PVD) in the amorphous phase on silicon substrates. We study in-situ, by X-ray and ultraviolet photoemission spectroscopies (XPS and UPS), the electronic properties and carefully ascertain the alloy composition to be GST 29 20 28. Subsequently, Raman spectroscopy is employed to corroborate the results from the photoemission study. X-ray diffraction is used upon annealing to study the crystallization of such an alloy and identify the effects of phase separation and segregation of crystalline Ge with the formation of grains along the [111] direction, as expected for such Ge-rich Ge-Sb-Te alloys. In addition, we report on the electrical characterization of single memory cells containing the Ge-rich Ge-Sb-Te alloy, including I-V characteristic curves, programming curves, and SET and RESET operation performance, as well as upon annealing temperature. A fair alignment of the electrical parameters with the current state-of-the-art of conventional (GeTe)n-(Sb2Te3)m alloys, deposited by PVD, is found, but with enhanced thermal stability, which allows for data retention up to 230 °C

Electron energy loss study of Ag- and Au-GaAs(110) interfaces

A high-resolution electron energy loss investigation of the Ag- and Au-GaAs(110) interfaces is presented. The loss spectra (0.5 less than or equal to E(loss) less than or equal to 5 eV) show clearly a broad feature centred at 1.2 eV, that is within the energy gap, due to the metal coverage. This structure, which starts appearing at coverages as low as 0.1 Angstrom, becomes undetectable at coverages of 24 Angstrom of Ag and 1.6 Angstrom of Au. The gap energy region has been examined on several freshly cleaved surfaces. In the case of bad cleaveges, a peak similar to that induced by the metal overlayer develops, a fact which supports mechanisms ascribing the Fermi level pinning to defect states