Tailoring chemical bonds to design unconventional glasses.

Glasses are commonly described as disordered counterparts of the corresponding crystals; both usually share the same short-range order, but glasses lack long-range order. Here, a quantification of chemical bonding in a series of glasses and their corresponding crystals is performed, employing two quantum-chemical bonding descriptors, the number of electrons transferred and shared between adjacent atoms. For popular glasses like SiO, GeSe, and GeSe, the quantum-chemical bonding descriptors of the glass and the corresponding crystal hardly differ.

Metavalent or Hypervalent Bonding: Is There a Chance for Reconciliation?

A family of solids including crystalline phase change materials such as GeTe and Sb Te , topological insulators like Bi Se and halide perovskites such as CsPbI possesses an unconventional property portfolio that seems incompatible with ionic, metallic, or covalent bonding. Instead, evidence is found for a bonding mechanism characterized by half-filled p-bands and a competition between electron localization and delocalization. Different bonding concepts have recently been suggested based on quantum chemical bonding descriptors which either define the bonds in these solids as electron-deficient (metavalent) or electron-rich (hypervalent).

Revisiting the Nature of Chemical Bonding in Chalcogenides to Explain and Design their Properties.

Quantum chemical bonding descriptors have recently been utilized to design materials with tailored properties. Their usage to facilitate a quantitative description of bonding in chalcogenides as well as the transition between different bonding mechanisms is reviewed. More importantly, these descriptors can also be employed as property predictors for several important material characteristics, including optical and transport properties.

Sub-Picosecond Non-Equilibrium States in the Amorphous Phase of GeTe Phase-Change Material Thin Films.

The sub-picosecond response of amorphous germanium telluride thin film to a femtosecond laser excitation is investigated using frequency-domain interferometry and ab initio molecular dynamics. The time-resolved measurement of the surface dynamics reveals a shrinkage of the film with a dielectric properties' response faster than 300 fs. The systematic ab initio molecular dynamics simulations in non-equilibrium conditions allow the atomic configurations to be retrieved for ionic temperature from 300 to 1100 K and width of the electron distribution from 0.

Metavalent Bonding in Crystalline Solids: How Does It Collapse?

The chemical bond is one of the most powerful, yet much debated concepts in chemistry, explaining property trends in solids. Recently, a novel type of chemical bonding was identified in several higher chalcogenides, characterized by a unique property portfolio, unconventional bond breaking, and sharing of about one electron between adjacent atoms. This metavalent bond is a fundamental type of bonding in solids, besides covalent, ionic, and metallic bonding, raising the pertinent question as to whether there is a well-defined transition between metavalent and covalent bonds.

Discovering Electron-Transfer-Driven Changes in Chemical Bonding in Lead Chalcogenides (PbX, where X = Te, Se, S, O).

Understanding the nature of chemical bonding in solids is crucial to comprehend the physical and chemical properties of a given compound. To explore changes in chemical bonding in lead chalcogenides (PbX, where X = Te, Se, S, O), a combination of property-, bond-breaking-, and quantum-mechanical bonding descriptors are applied. The outcome of the explorations reveals an electron-transfer-driven transition from metavalent bonding in PbX (X = Te, Se, S) to iono-covalent bonding in β-PbO.

Laser Generation of Sub-Micrometer Wrinkles in a Chalcogenide Glass Film as Physical Unclonable Functions.

Laser interaction with solids is routinely used for functionalizing materials' surfaces. In most cases, the generation of patterns/structures is the key feature to endow materials with specific properties like hardening, superhydrophobicity, plasmonic color-enhancement, or dedicated functions like anti-counterfeiting tags. A way to generate random patterns, by means of generation of wrinkles on surfaces resulting from laser melting of amorphous Ge-based chalcogenide thin films, is presented.

Toward ultimate nonvolatile resistive memories: The mechanism behind ovonic threshold switching revealed.

Fifty years after its discovery, the ovonic threshold switching (OTS) phenomenon, a unique nonlinear conductivity behavior observed in some chalcogenide glasses, has been recently the source of a real technological breakthrough in the field of data storage memories. This breakthrough was achieved because of the successful 3D integration of so-called OTS selector devices with innovative phase-change memories, both based on chalcogenide materials. This paves the way for storage class memories as well as neuromorphic circuits.

Understanding the Structure and Properties of Sesqui-Chalcogenides (i.e., V VI or Pn Ch (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective.

A number of sesqui-chalcogenides show remarkable properties, which make them attractive for applications as thermoelectrics, topological insulators, and phase-change materials. To see if these properties can be related to a special bonding mechanism, seven sesqui-chalcogenides (Bi Te , Bi Se , Bi S , Sb Te , Sb Se , Sb S , and β-As Te ) and GaSe are investigated. Atom probe tomography studies reveal that four of the seven sesqui-chalcogenides (Bi Te , Bi Se , Sb Te , and β-As Te ) show an unconventional bond-breaking mechanism.

A Quantum-Mechanical Map for Bonding and Properties in Solids.

A 2D map is created for solid-state materials based on a quantum-mechanical description of electron sharing and electron transfer. This map intuitively identifies the fundamental nature of ionic, metallic, and covalent bonding in a range of elements and binary compounds; furthermore, it highlights a distinct region for a mechanism recently termed "metavalent" bonding. Then, it is shown how this materials map can be extended in the third dimension by including physical properties of application interest.

Incipient Metals: Functional Materials with a Unique Bonding Mechanism.

While solid-state materials are commonly classified as covalent, ionic, or metallic, there are cases that defy these iconic bonding mechanisms. Phase-change materials (PCMs) for data storage are a prominent example: they have been claimed to show "resonant bonding," but a clear definition of this mechanism has been lacking. Here, it is shown that these solids are fundamentally different from resonant bonding in the π-orbital systems of benzene and graphene, based on first-principles data for vibrational, optical, and polarizability properties.

Decoding entangled transitions: Polyamorphism and stressed rigidity.

There is much to learn from simulation studies of polyamorphism achieved for systems with different bonding environments. Chalcogenide glasses such as Ge-Se glasses undergo an elastic phase transition involving important changes in network connectivity. Stimulated by recent developments of topological constraint theory, we show that the concept of rigidity can be extended to a broader range of thermodynamic conditions including densified glasses.

Anomalous diffusion and non-monotonic relaxation processes in Ge-Se liquids.

We investigate the dynamical properties of liquid GexSe100-x as a function of Ge content by first-principles molecular dynamic simulations for a certain number of temperatures in the liquid state. The focus is set on ten compositions (where x ≤ 33%) encompassing the reported flexible to rigid and rigid to stressed-rigid transitions. We examine diffusion coefficients, diffusion activation energies, glassy relaxation behavior, and viscosity of these liquids from Van Hove correlation and intermediate scattering functions.

Universal amorphous-amorphous transition in GexSe100-x glasses under pressure.

Pressure induced structural modifications in vitreous GexSe100-x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa.

Aging mechanisms in amorphous phase-change materials.

Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments.

Dynamics of the negative thermal expansion in tellurium based liquid alloys.

Negative thermal expansion (NTE) in tellurium based liquid alloys (GeTe6 and GeTe12) is analyzed through the atomic vibrational properties. Using neutron inelastic scattering, we show that the structural evolution resulting in the NTE is due to a gain of vibrational entropy that cancels out the Peierls distortion. In the NTE temperature range, these competing effects give rise to noticeable changes in the vibrational density of states spectra.

Tetrahedral clustering in molten lithium under pressure.

A series of electronic and structural transitions are predicted in molten lithium from first principles. A new phase with tetrahedral local order characteristic of sp3 bonded materials and poor electrical conductivity is found at pressures above 150 GPa and temperatures as high as 1000 K. Despite the lack of covalent bonding, weakly bound tetrahedral clusters with finite lifetimes are predicted to exist.

Electronic and structural transitions in dense liquid sodium.

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures.

Temperature-induced density anomaly in Te-Rich liquid germanium tellurides: p versus sp3 bonding?

The density anomaly of liquid Ge(0.15)Te(0.85) measured between 633 and 733 K is investigated with ab initio molecular dynamics calculations at four temperatures and at the corresponding experimental densities.

Growth of carbon nanotubes on metal nanoparticles: a microscopic mechanism from ab initio molecular dynamics simulations.

We report on ab initio molecular dynamics simulations of the early stages of single-walled carbon nanotube (SWCNT) growth on metal nanoparticles. Our results show that a sp2 bonded cap is formed on an iron catalyst, following the diffusion of C atoms from hydrocarbon precursors on the nanoparticle surface. The weak adhesion between the cap and iron enables the graphene sheet to "float" on the curved surface, as additional C atoms covalently bonded to the catalyst "hold" the tube walls.

Ultradispersity of diamond at the nanoscale.

Nanometre-sized diamond has been found in meteorites, protoplanetary nebulae and interstellar dusts, as well as in residues of detonation and in diamond films. Remarkably, the size distribution of diamond nanoparticles seems to be peaked around 2-5 nm, and to be largely independent of preparation conditions. We have carried out ab initio calculations of the stability of nanodiamond as a function of surface hydrogen coverage and of size.

Quantum confinement and fullerenelike surface reconstructions in nanodiamonds.

We present x-ray absorption and emission experiments and ab initio calculations showing that the size of carbon diamond must be reduced to at least 2 nm, in order to observe an increase of its optical gap, at variance with Si and Ge where quantum confinement effects persist up to 6-7 nm. In addition, our calculations show that the surface of nanodiamond particles larger than approximately 1 nm reconstructs in a fullerenelike manner, giving rise to a new family of carbon clusters: bucky diamonds. Signatures of these surface reconstructions are compatible with pre-edge features observed in measured absorption spectra.

Adsorption of selenium wires in silicalite-1 zeolite: a first order transition in a microporous system.

A tight binding grand canonical Monte Carlo simulation of the adsorption of selenium in silicalite-1 zeolite is presented. The calculated adsorption-desorption isotherms exhibit characteristic features of a first order transition, unexpected for adsorption in a microporous system with pore size of the order of 0.5 to 0.