Decoding the Atomic Structure of Ga2Te5 Pulsed Laser Deposition Films for Memory Applications Using Diffraction and First-Principles Simulations.

Neuromorphic computing, reconfigurable optical metamaterials that are operational over a wide spectral range, holographic and nonvolatile displays of extremely high resolution, integrated smart photonics, and many other applications need next-generation phase-change materials (PCMs) with better energy efficiency and wider temperature and spectral ranges to increase reliability compared to current flagship PCMs, such as Ge2Sb2Te5 or doped Sb2Te. Gallium tellurides are favorable compounds to achieve the necessary requirements because of their higher melting and crystallization temperatures, combined with low switching power and fast switching rate. Ga2Te3 and non-stoichiometric alloys appear to be atypical PCMs; they are characterized by regular tetrahedral structures and the absence of metavalent bonding. The sp3 gallium hybridization in cubic and amorphous Ga2Te3 is also different from conventional p-bonding in flagship PCMs, raising questions about its phase-change mechanism. Furthermore, gallium tellurides exhibit a number of unexpected and highly unusual phenomena, such as nanotectonic compression and viscosity anomalies just above their melting points. Using high-energy X-ray diffraction, supported by first-principles simulations, we will elucidate the atomic structure of amorphous Ga2Te5 PLD films, compare it with the crystal structure of tetragonal gallium pentatelluride, and investigate the electrical, optical, and thermal properties of these two materials to assess their potential for memory applications, among others.

Deciphering Fast Ion Transport in Glasses: A Case Study of Sodium and Silver Vitreous Sulfides.

High-capacity solid-state batteries are promising future products for large-scale energy storage and conversion. Sodium fast ion conductors including glasses and glass ceramics are unparalleled materials for these applications. Rational design and tuning of advanced sodium sulfide electrolytes need a deep insight into the atomic structure and dynamics in relation with ion-transport properties. Using pulsed neutron diffraction and Raman spectroscopy supported by first-principles simulations, we show that preferential diffusion pathways in vitreous sodium and silver sulfides are related to isolated sulfur Siso, that is, the sulfur species surrounded exclusively by mobile cations with a typical stoichiometry of M/Siso ≈ 2. The Siso/Stot fraction appears to be a reliable descriptor of fast ion transport in glassy sulfide systems over a wide range of ionic conductivities and cation diffusivities. The Siso fraction increases with mobile cation content x, tetrahedral coordination of the network former and, in case of thiogermanate systems, with germanium disulfide metastability and partial disproportionation, GeS2 → GeS + S, leading to the formation of additional sulfur, transforming into Siso. A research strategy enabling to achieve extended and interconnected pathways based on isolated sulfur would lead to glassy electrolytes with superior ionic diffusion.

Unraveling the Atomic Structure of Bulk Binary Ga-Te Glasses with Surprising Nanotectonic Features for Phase-Change Memory Applications.

Binary Ge-Te and ternary Ge-Sb-Te systems belong to flagship phase-change materials (PCMs) and are used in nonvolatile memory applications and neuromorphic computing. The working temperatures of these PCMs are limited by low-T glass transition and crystallization phenomena. Promising high-T PCMs may include gallium tellurides; however, the atomic structure and transformation processes for amorphous Ga-Te binaries are simply missing. Using high-energy X-ray diffraction and Raman spectroscopy supported by first-principles simulations, we elucidate the short- and intermediate-range order in bulk glassy GaxTe1-x, 0.17 ≤ x ≤ 0.25, following their thermal, electric, and optical properties, revealing a semiconductor-metal transition above melting. We also show that a phase change in binary Ga-Te is characterized by a very unusual nanotectonic compression with the high internal transition pressure reaching 4-8 GPa, which appears to be beneficial for PCM applications increasing optical and electrical contrast between the SET and RESET states and decreasing power consumption.

Glassy GaS: transparent and unusually rigid thin films for visible to mid-IR memory applications.

Phase-change materials based on tellurides are widely used for optical storage (DVD and Blu-ray disks), non-volatile random access memories and for development of neuromorphic computing. Narrow-gap tellurides are intrinsically limited in the telecom spectral window, where materials having a wider gap are needed. Here we show that gallium sulfide GaS thin films prepared by pulsed laser deposition reveal good transparency from the visible to the mid-IR spectral range with optical gap Eg = 2.34 eV, high refractive index nR = 2.50 over the 0.8 ≤ λ ≤ 2.5 µm range and, unlike canonical chalcogenide glasses, the absence of photo-structural transformations with a laser-induced peak power density damage threshold above 1.4 TW cm-2 at 780 nm. The origin of the excellent damage threshold under a high-power laser and UV light irradiation resides in the rigid tetrahedral structure of vitreous GaS studied by high-energy X-ray diffraction and Raman spectroscopy and supported by first-principles simulations. The average local coordination number appears to be m = 3.44, well above the optimal connectivity, 2.4 ≤ m ≤ 2.7, and the total volume of microscopic voids and cavities is 34.4%, that is, lower than for the vast majority of binary sulfide glasses. The glass-crystal phase transition in gallium sulfide thin films may be accompanied by a drastic change in the nonlinear optical properties, opening up a new dimension for memory applications in the visible to mid-IR spectral ranges.

Chemical and Structural Variety in Sodium Thioarsenate Glasses Studied by Neutron Diffraction and Supported by First-Principles Simulations.

Sodium-conducting sulfide glasses are promising materials for the next generation of solid-state batteries. Deep insight into the glass structure is required to ensure a functional design and tailoring of vitreous alloys for energy applications. Using pulsed neutron diffraction supported by first-principles molecular dynamics, we show a structural diversity of Na2S-As2S3 sodium thioarsenate glasses, consisting of long corner-sharing (CS) pyramidal chains CS-(AsSS2/2)k, small AspSq rings (p + q ≤ 11), mixed corner- and edge-sharing oligomers, edge-sharing (ES) dimers ES-As2S4, and isolated (ISO) pyramids ISO-AsS3, entirely or partially connected by sodium species. Polysulfide S-S bridges and structural units with homopolar As-As bonds complete the glass structure, which is basically different from structural motifs predicted by the equilibrium phase diagram. In contrast to superionic silver and sodium sulfide glasses, characterized by a significant population of isolated sulfur species Siso (0.20 < Siso/Stot < 0.28), that is, sulfur connected to only mobile cations M+ with a usual M/Siso stoichiometry of 2, poorly conducting Na2S-As2S3 alloys exhibit a modest Siso fraction of 6.2%.

Full Conformational Landscape of 3-Methoxyphenol Revealed by Room Temperature mm-wave Rotational Spectroscopy Supported by Quantum Chemical Calculations.

Room temperature millimeter-wave rotational spectroscopy supported by high level of theory calculations have been employed to fully characterise the conformational landscape of 3-Methoxyphenol, a semi-volatile polar oxygenated aromatic compound precursor of secondary organic aerosols in the atmosphere arising from biomass combustion. While previous rotationally-resolved spectroscopic studies in the microwave and in the UV domains failed to observe the complete conformational landscape, the 70-330 GHz rotational spectrum measured in this study reveals the ground state rotational signatures of the four stable conformations theoretically predicted. Moreover, rotational transitions in the lowest energy vibrationally excited states were assigned for two conformers. While the inertial defect of methoxyphenol does not significantly change between conformers and isomers, the excitation of the methoxy out-of-plane bending is the main contribution to the non-planarity of the molecule.

High resolution study of the ν2 and ν5 rovibrational fundamental bands of thionyl chloride: Interplay of an evolutionary algorithm and a line-by-line analysis.

The ν2 and ν5 fundamental bands of thionyl chloride (SOCl2) were measured in the 420 cm-1-550 cm-1 region using the FT-far-IR spectrometer exploiting synchrotron radiation on the AILES beamline at SOLEIL. A straightforward line-by-line analysis is complicated by the high congestion of the spectrum due to both the high density of SOCl2 rovibrational bands and the presence of the ν2 fundamental band of sulfur dioxide produced by hydrolysis of SOCl2 with residual water. To overcome this difficulty, our assignment procedure for the main isotopologues 32S16O35Cl2 and 32S16O35Cl37Cl alternates between a direct fit of the spectrum, via a global optimization technique, and a traditional line-by-line analysis. The global optimization, based on an evolutionary algorithm, produces rotational constants and band centers that serve as useful starting values for the subsequent spectroscopic analysis. This work helped to identify the pure rotational submillimeter spectrum of 32S16O35Cl2 in the v2=1 and v5=1 vibrational states of Martin-Drumel et al. [J. Chem. Phys. 144, 084305 (2016)]. As a by-product, the rotational transitions of the v4=1 far-IR inactive state were identified in the submillimeter spectrum. A global fit gathering all the microwave, submillimeter, and far-IR data of thionyl chloride has been performed, showing that no major perturbation of rovibrational energy levels occurs for the main isotopologue of the molecule.