Geometry of tellurene adsorbed on the Si(111)-R30°-Sb surface from first principles calculations.

The 2D form of tellurium, named tellurene, is one of the latest discoveries in the family of 2D mono-elemental materials. In a trilayer configuration, free-standing tellurene was predicted theoretically to acquire two crystallographic forms, the α and ß phases, corresponding to either a 1T-MoS2-like geometry or a trilayer slab exposing the Te(101̄0) surface of bulk Te with helical chains lying in-plane and further reconstructed due to the formation of interchain bonds. Either one or the other of the two phases was observed experimentally to prevail depending on the substrate they were grown onto. In the perspective to integrate tellurene on silicon, we here report an ab initio study of the adsorption of tellurene on the Si(111)-R30° surface passivated by antinomy. According to the literature, this substrate is chosen for the growth of several tellurides by molecular beam epitaxy. The calculations reveal that on this substrate the adsorption energy mostly compensates the energy difference between the α and ß phases in the free-standing configuration which suggests that the prevalence of one phase over the other might in this case strongly depend on the kinetics effects and deposition conditions.

Priming effects in the crystallization of the phase change compound GeTe from atomistic simulations.

Strategies to reduce the incubation time for crystal nucleation and thus the stochasticity of the set process are of relevance for the operation of phase change memories in ultra-scaled geometries. With these premises, in this work we investigate the crystallization kinetics of the phase change compound GeTe. We have performed large scale molecular dynamics simulations using an interatomic potential, generated previously from a neural network fitting of a database of ab initio energies. We have addressed the crystallization of models of amorphous GeTe annealed at different temperatures above the glass transition. The results on the distribution of subcritical nuclei and on the crystal growth velocity of postcritical ones are compared with our previous simulations of the supercooled liquid quenched from the melt. We find that a large population of subcritical nuclei can form at the lower temperatures where the nucleation rate is large. This population partially survives upon fast annealing, which leads to a dramatic reduction of the incubation time at high temperatures where the crystal growth velocity is maximal. This priming effect could be exploited to enhance the speed of the set process in phase change memories.

Structural and electronic properties of liquid, amorphous, and supercooled liquid phases of In2Te5 from first-principles.

In2Te5 is a stoichiometric compound in the In-Te system of interest for applications in phase change electronic memories and thermoelectrics. Here, we perform a computational study of the structural, dynamical, and electronic properties of the liquid, supercooled liquid, and amorphous phases of this compound by means of density functional molecular dynamics simulations. Models of the supercooled liquid and amorphous phases have been generated by quenching from the melt. The structure of the liquid phase is characterized by a mixture of defective octahedral and tetrahedral local environments of In atoms, while the amorphous phase displays a mostly tetrahedral local geometry for In atoms with corner and edge sharing tetrahedra similar to those found in the crystalline phases of the In2Te5, InTe, and In2Te3 compounds. Comparison with our previous results on liquid and amorphous In2Te3 and further data on the structural properties of liquid In2Te3 are also discussed. The analysis of the electronic properties highlights the opening of a mobility gap in In2Te5 at about 150 K below the liquidus temperature.

Prebiotic NH3 Formation: Insights from Simulations.

Simulations of prebiotic NH3 synthesis from NO3⁻ and NO2⁻ on pyrite surfaces under hydrothermal conditions are reported. Ab initio metadynamics calculations have successfully explored the full reaction path which explains earlier experimental observations. We have found that the reaction mechanism can be constructed from stepwise single atom transfers which are compatible with the expected reaction time scales. The roles of the hot-pressurized water and of the pyrite surfaces have been addressed. The mechanistic picture that emerged from the simulations strengthens the theory of chemoautotrophic origin of life by providing plausible reaction pathways for the formation of ammonia within the iron-sulfur-world scenario.

Influence of the exchange and correlation functional on the structure of amorphous InSb and In3SbTe2 compounds.

We have investigated the structural, vibrational, and electronic properties of the amorphous phase of InSb and In3SbTe2 compounds of interest for applications in phase change non-volatile memories. Models of the amorphous phase have been generated by quenching from the melt by molecular dynamics simulations based on density functional theory. In particular, we have studied the dependence of the structural properties on the choice of the exchange-correlation functional. It turns out that the use of the Becke-Lee-Yang-Parr functional provides models with a much larger fraction of In atoms in a tetrahedral bonding geometry with respect to previous results obtained with the most commonly used Perdew-Becke-Ernzerhof functional. This outcome is at odd with the properties of Ge2Sb2Te5 phase change compound for which the two exchange-correlation functionals yield very similar results on the structure of the amorphous phase.

Pyrite in contact with supercritical water: the desolation of steam.

The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.

Crystallization kinetics of nanoconfined GeTe slabs in GeTe/TiTe[Formula: see text]-like superlattices for phase change memories.

Superlattices made of alternating blocks of the phase change compound Sb[Formula: see text]Te[Formula: see text] and of TiTe[Formula: see text] confining layers have been recently proposed for applications in neuromorphic devices. The Sb[Formula: see text]Te[Formula: see text]/TiTe[Formula: see text] heterostructure allows for a better control of multiple intermediate resistance states and for a lower drift with time of the electrical resistance of the amorphous phase. However, Sb[Formula: see text]Te[Formula: see text] suffers from a low data retention due to a low crystallization temperature T[Formula: see text]. Substituting Sb[Formula: see text]Te[Formula: see text] with a phase change compound with a higher T[Formula: see text], such as GeTe, seems an interesting option in this respect. Nanoconfinement might, however, alters the crystallization kinetics with respect to the bulk. In this work, we investigated the crystallization process of GeTe nanoconfined in geometries mimicking GeTe/TiTe[Formula: see text] superlattices by means of molecular dynamics simulations with a machine learning potential. The simulations reveal that nanoconfinement induces a mild reduction in the crystal growth velocities which would not hinder the application of GeTe/TiTe[Formula: see text] heterostructures in neuromorphic devices with superior data retention.

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

The possibility to engineer (GeTe)m (Sb2 Te3 )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 (Sb2 Te3 )n with GeTe-rich composition is presented. These layered films feature a tunable distribution of (GeTe)m (Sb2 Te3 )1 blocks of different sizes. Breakthrough evidence of ferroelectric displacement in thick (GeTe)m (Sb2 Te3 )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.

Infections with the microbe Cardinium in the Dolichopodidae and other Empidoidea.

Maternally transmitted reproductive parasites such as Wolbachia and Cardinium can drastically reshape reproduction in their hosts. Beyond skewing sex ratios towards females, these microbes can also cause cytoplasmic incompatibility. Wolbachia probably infects two thirds of insects, but far less is known about the occurrence or action of other bacteria with potentially similar effects. In contrast with the two more widespread reproductive parasites, Wolbachia and Spiroplasma, far less is known of infections with Cardinium (Bacteroidetes) and possible consequences in the Diptera. Here, in an extensive survey, 244 dipteran species from 67 genera belonging to the Dolichopodidae, Empididae, and Hybotidae were assessed for the presence of the microbe Cardinium. Although 130 of the species screened tested positive (ca. 53%), the presence of Cardinium could only be confirmed in 10 species (ca. 4%) based on analysis of sequences. Numerous additional sequences were found to be assignable to known or unknown Bacteroidetes. Considering the known issues concerning specificity of Cardinium primers and the phylogenetic uncertainties surrounding this microbe, the actual prevalence of this symbiont is worthy of further scrutiny. Potential directions for future research on Cardinium-host interactions in Diptera and in general are discussed.

The Palaearctic types of Chrysididae (Insecta, Hymenoptera) deposited in the Linsenmaier collection. Part 4. Elampini: genus Omalus Panzer, 1801.

An illustrated catalogue of the Palaearctic types of species and subspecies described by Walter Linsenmaier in Omalus Panzer, 1801 is given. Linsenmaier described 16 species and subspecies of Omalus; most of the primary types are deposited in the collection at the Natur-Museum in Luzern, Switzerland, with the exception of four holotypes which are deposited at the Natural History Museum in London, UK; Nationalparkzentrum in Zernez, Switzerland; Eidgenössische Technische Hochschule in Zurich, Switzerland; and Museo de Naturaleza y Arqueologia in St. Cruz de Tenerife, Spain. A list of the species described and pictures of 13 primary and secondary types are presented. A synthesis of his classification is given, with comments and comparison to modern classification.

The use of autologous bone for augmentation procedures leads to low prevalence of peri-implantitis-a retrospective study over a 20-year period.

The aim of this study was to compare the prevalence of peri-implantitis in implants inserted into pristine bone (control) to implants where autologous bone was used for grafting procedures (study). All patients who underwent implant surgery during a 20 years interval by one maxillofacial implant surgeon and received a prosthodontic rehabilitation afterwards were eligible for inclusion in the study. Periimplant bone resorption and periimplant disease were assessed. Of 421 patients 384 (91.2%) patients responded to a recall after having been treated over a 20-year period by one maxillofacial surgeon and several dentists. A total of 110 patients had 239 implants in pristine bone, and 274 patients had 607 implants placed in combination with autologous bone grafting procedures. Mean time in function was 74 months (range 15-236 months). In all, 342 implants (34.8%) were in function for longer than 7 years. A total of 64 implant sites (7.6%) in 39 patients (10.2%) showed signs of peri-implant mucositis. In addition, 17 implants (2.0%) in 14 patients (3.6%) revealed signs of peri-implantitis, of which five implants were in the control group (2.09%) whereas 12 implants were in the study group (1.98%), with no statistically significant difference (p = 0.8405). More than half of the patients with peri-implantitis had a history of periodontitis. Three implants were lost due to peri-implantitis and four implants failed for other reasons, resulting in an overall success rate of 99.2% in 846 implants. CONCLUSIONS: Within the limitations of the study it seems that the use of autologous bone still is a relevant option when performing augmentation procedures because of the low prevalence of peri-implantitis.

Pressure-induced reversal of Peierls-like distortions elicits the polyamorphic transition in GeTe and GeSe.

While polymorphism is prevalent in crystalline solids, polyamorphism draws increasing interest in various types of amorphous solids. Recent studies suggested that supercooling of liquid phase-change materials (PCMs) induces Peierls-like distortions in their local structures, underlying their liquid-liquid transitions before vitrification. However, the mechanism of how the vitrified phases undergo a possible polyamorphic transition remains elusive. Here, using high-energy synchrotron X-rays, we can access the precise pair distribution functions under high pressure and provide clear evidence that pressure can reverse the Peierls-like distortions, eliciting a polyamorphic transition in GeTe and GeSe. Combined with simulations based on machine-learned-neural-network potential, our structural analysis reveals a high-pressure state characterized by diminished Peierls-like distortion, greater coherence length, reduced compressibility, and a narrowing bandgap. Our finding underscores the crucial role of Peierls-like distortions in amorphous octahedral systems including PCMs. These distortions can be controlled through pressure and composition, offering potentials for designing properties in PCM-based devices.

The Palaearctic types of Chrysididae (Insecta, Hymenoptera) deposited in the Linsenmaier collection. Part 2. Elampini: genus Hedychridium Abeille de Perrin, 1878.

An illustrated catalogue of the Palaearctic types of species and subspecies described by Walter Linsenmaier in the genus Hedychridium Abeille de Perrin, 1878 is given. Linsenmaier described 110 species and subspecies of Hedychridium, most of the holotypes are deposited in his collection, at the Natur-Museum (Luzern, Switzerland), with the exception of 25 holotypes which are deposited at the Bristish Museum (London), at the Muse cantonal de zoologie (Lausanne) and in two private collections. Hedychridium atratum is here transferred to Chamaeholopyga Linsenmaier, 1987. Hedychridium krajniki turceyense Linsenmaier, 1968 stat. nov. is upgraded to species rank. The holotype of Hedychridium caireanum Linsenmaier, 1968 is considered lost. A list of the species described and a synthesys of his classification is given. Pictures of 83 primary and secondary types are presented.

The Palaearctic types of Chrysididae (Insecta, Hymenoptera) deposited in the Linsenmaier collection. Part 3. Elampini: genus Hedychrum Latreille.

An illustrated catalogue of the Palaearctic types of species and subspecies described by Walter Linsenmaier in the genus Hedychrum Latreille, 1802 is given. Linsenmaier described 14 taxa of Hedychrum; almost all primary types are deposited in the collection, at the Natur Museum (Luzern, Switzerland), with the exception of two holotypes which are deposited at the Natural History Museum (London), and Naturalis (Leiden). Hedychrum mithras Semenov-Tian-Shanskij, 1967 spec. resurr. is revalidated from the previous synonymy with Hedychrum luculentum bytinskii Linsenmaier, 1959. A list of the species described and pictures of the holotypes and allotypes deposited in the collection are given.

Extreme Bendability of Atomically Thin MoS2 Grown by Chemical Vapor Deposition Assisted by Perylene-Based Promoter.

Shaping two-dimensional (2D) materials in arbitrarily complex geometries is a key to designing their unique physical properties in a controlled fashion. This is an elegant solution, taking benefit from the extreme flexibility of the 2D layers but requiring the ability to force their spatial arrangement from flat to curved geometries in a delicate balance among free-energy contributions from strain, slip-and-shear mechanisms, and adhesion to the substrate. Here, we report on a chemical vapor deposition approach, which takes advantage of the surfactant effects of organic molecules, namely the tetrapotassium salt of perylene-3,4,9,10-tetracarboxylic acid (PTAS), to conformally grow atomically thin layers of molybdenum disulphide (MoS2) on arbitrarily nanopatterned substrates. Using atomically resolved transmission electron microscope images and density functional theory calculations, we show that the most energetically favorable condition for the MoS2 layers consists of its adaptation to the local curvature of the patterned substrate through a shear-and-slip mechanism rather than strain accumulation. This conclusion also reveals that the perylene-based molecules have a role in promoting the adhesion of the layers onto the substrate, no matter the local-scale geometry.

Phase Separation in Ge-Rich GeSbTe at Different Length Scales: Melt-Quenched Bulk versus Annealed Thin Films.

Integration of the prototypical GeSbTe (GST) ternary alloys, especially on the GeTe-Sb2Te3 tie-line, into non-volatile memory and nanophotonic devices is a relatively mature field of study. Nevertheless, the search for the next best active material with outstanding properties is still ongoing. This search is relatively crucial for embedded memory applications where the crystallization temperature of the active material has to be higher to surpass the soldering threshold. Increasing the Ge content in the GST alloys seems promising due to the associated higher crystallization temperatures. However, homogeneous Ge-rich GST in the as-deposited condition is thermodynamically unstable, and phase separation upon annealing is unavoidable. This phase separation reduces endurance and is detrimental in fully integrating the alloys into active memory devices. This work investigated the phase separation of Ge-rich GST alloys, specifically Ge5Sb2Te3 or GST523, into multiple (meta)stable phases at different length scales in melt-quenched bulk and annealed thin film. Electron microscopy-based techniques were used in our work for chemical mapping and elemental composition analysis to show the formation of multiple phases. Our results show the formation of alloys such as GST213 and GST324 in all length scales. Furthermore, the alloy compositions and the observed phase separation pathways agree to a large extent with theoretical results from density functional theory calculations.

Crystallization and Electrical Properties of Ge-Rich GeSbTe Alloys.

Enrichment of GeSbTe alloys with germanium has been proposed as a valid approach to increase the crystallization temperature and therefore to address high-temperature applications of non-volatile phase change memories, such as embedded or automotive applications. However, the tendency of Ge-rich GeSbTe alloys to decompose with the segregation of pure Ge still calls for investigations on the basic mechanisms leading to element diffusion and compositional variations. With the purpose of identifying some possible routes to limit the Ge segregation, in this study, we investigate Ge-rich Sb2Te3 and Ge-rich Ge2Sb2Te5 with low (<40 at %) or high (>40 at %) amounts of Ge. The formation of the crystalline phases has been followed as a function of annealing temperature by X-ray diffraction. The temperature dependence of electrical properties has been evaluated by in situ resistance measurements upon annealing up to 300 °C. The segregation and decomposition processes have been studied by scanning transmission electron microscopy (STEM) and discussed on the basis of density functional theory calculations. Among the studied compositions, Ge-rich Ge2Sb2Te5 is found to be less prone to decompose with Ge segregation.