Emmanuel Soignard

Vibrational spectroscopy in the electron microscope

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample—that is, for ‘aloof’ spectroscopy that largely avoids radiation damage.

Vitrification of a monatomic metallic liquid

Although the majority of glasses in use in technology are complex mixtures of oxides or chalcogenides, there are numerous examples of pure substances—‘glassformers’—that also fail to crystallize during cooling. Most glassformers are organic molecular systems, but there are important inorganic examples too, such as silicon dioxide and elemental selenium (the latter being polymeric). Bulk metallic glasses can now be made; but, with the exception of Zr50Cu50 (ref. 4), they require multiple components to avoid crystallization during normal liquid cooling. Two-component ‘metglasses’ can often be achieved by hyperquenching, but this has not hitherto been achieved with a single-component system. Glasses form when crystal nucleation rates are slow, although the factors that create the slow nucleation conditions are not well understood. Here we apply the insights gained in a recent molecular dynamics simulation study to create conditions for successful vitrification of metallic liquid germanium. Our results also provide micrographic evidence for a rare polyamorphic transition preceding crystallization of the diamond cubic phase.

High pressure-high temperature synthesis and elasticity of the cubic nitride spinel γ-Si3N4

The compressional behaviour of a new dense form of silicon nitride with the cubic spinel structure is studied by energy dispersive x-ray diffraction, following in situ synthesis from the low pressure form by laser heating in the diamond anvil cell, combined with theoretical density functional calculations (LDA and GGA). The unit cell dimension and the ambient temperature bulk modulus and its pressure derivative are determined to be V0 = 8.29(±0.03) A 3 /atom, K0 = 308(±5) GPa and K � 0 = 4±(0.2), in excellent agreement with theoretical calculations within the LDA and GGA. The calculated shear modulus is two to three times those of corresponding oxide spinels, and there is a substantial Cauchy violation, indicating a material with strong covalent bonding that is likely to be extremely hard.

Cell assemblies for reproducible multi-anvil experiments (the COMPRES assemblies)

Abstract The multi-anvil high-pressure technique is an important tool in high-pressure mineralogy and petrology, as well as in chemical synthesis, allowing the treatment of large (millimeter-size) samples of minerals, rocks, and other materials at pressures of a few GPa to over 25 GPa and simultaneous uniform temperatures up to 2500 °C and higher. A series of cell assemblies specially designed and implemented for interlaboratory use are described here. In terms of the size of the pressure medium and the anvil truncation size, the five sizes of assemblies developed here are an 8/3, 10/5, 14/8, 18/12, and 25/15 assembly. As of this writing, these assemblies are in widespread use at many laboratories. The details of design, construction, and materials developed or used for the assemblies are presented here.

Thermal decomposition of ammonia borane at high pressures

The effects of high pressure (up to 9 GPa) on the thermal decomposition of ammonia borane, BH3NH3, were studied in situ by Raman spectroscopy in a diamond anvil cell. In contrast with the three-step decomposition at ambient pressure, thermolysis under pressure releases almost the entire hydrogen content of the molecule in two distinct steps. The residual of the first decomposition is polymeric aminoborane, (BH2NH2)x, which is also observed at ambient pressure. The residual after the second decomposition is unique to high pressure. Presumably it corresponds to a precursor to hexagonal BN where macromolecular fragments of planar hexagon layers formed by B and N atoms are terminated by H atoms. Increasing pressure increases the temperature of both decomposition steps. Due to the increased first decomposition temperature it becomes possible to observe a new high pressure, high temperature phase of BH3NH3 which may represent melting.

Domain Architectures and Grain Boundaries in Chemical Vapor Deposited Highly Anisotropic ReS2 Monolayer Films

Recent studies have shown that vapor phase synthesis of structurally isotropic two-dimensional (2D) MoS2 and WS2 produces well-defined domains with clean grain boundaries (GBs). This is anticipated to be vastly different for 2D anisotropic materials like ReS2 mainly due to large anisotropy in interfacial energy imposed by its distorted 1T crystal structure and formation of signature Re-chains along [010] b-axis direction. Here, we provide first insight on domain architecture on chemical vapor deposited (CVD) ReS2 domains using high-resolution scanning transmission electron microscopy, angle-resolved nano-Raman spectroscopy, reflectivity, and atomic force microscopy measurements. Results provide ways to achieve crystalline anisotropy in CVD ReS2, establish domain architecture of high symmetry ReS2 flakes, and determine Re-chain orientation within subdomains. Results also provide a first atomic resolution look at ReS2 GBs, and surprisingly we find that cluster and vacancy defects, formed by collusion of Re-chains at the GBs, dramatically impact the crystal structure by changing the Re-chain direction and rotating Re-chains 180° along their b-axis. Overall results not only shed first light on domain architecture and structure of anisotropic 2D systems but also allow one to attain much desired crystalline anisotropy in CVD grown ReS2 for the first time for tangible applications in photonics and optoelectronics where direction-dependent dichroic and linearly polarized material properties are required.

A perforated diamond anvil cell for high-energy x-ray diffraction of liquids and amorphous solids at high pressure

Diamond anvil cells (DACs) are widely used for the study of materials at high pressure. The typical diamonds used are between 1 and 3 mm thick, while the sample contained within the opposing diamonds is often just a few microns in thickness. Hence, any absorbance or scattering from diamond can cause a significant background or interference when probing a sample in a DAC. By perforating the diamond to within 50-100 microm of the sample, the amount of diamond and the resulting background or interference can be dramatically reduced. The DAC presented in this article is designed to study amorphous materials at high pressure using high-energy x-ray scattering (>60 keV) using laser-perforated diamonds. A small diameter perforation maintains structural integrity and has allowed us to reach pressures >50 GPa, while dramatically decreasing the intensity of the x-ray diffraction background (primarily Compton scattering) when compared to studies using solid diamonds. This cell design allows us for the first time measurement of x-ray scattering from light (low Z) amorphous materials. Here, we present data for two examples using the described DAC with one and two perforated diamond geometries for the high-pressure structural studies of SiO(2) glass and B(2)O(3) glass.

High-pressure cells for in situ multi-anvil experiments

A new series of high-pressure cells for in situ multi-anvil experiments is described. The cells are based on the conventional COMPRES cells, but modifications are made to improve the passage of X-rays. The modifications include cutting slits in parts of the assemblies that have very high X-ray absorption, such as lanthanum chromite and rhenium, the use of low-Z thermal insulation, such as forsterite, in place of zirconia, and the partial replacement of zirconia by MgO equatorial windows combined with a mullite octahedron. Details of the designs, thermal characterizations, and examples of the application of these cells are described.

Unusual lattice vibration characteristics in whiskers of the pseudo-one-dimensional titanium trisulfide TiS3

Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS3) whiskers are made out of weakly interacting TiS3 layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS3 both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS3 have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the AgS–S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS3 with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.

Band Engineering by Controlling vdW Epitaxy Growth Mode in 2D Gallium Chalcogenides

Atomically thin quasi-2D GaSe flakes are synthesized via van der Waals (vdW) epitaxy on a polar Si (111) surface. The bandgap is continuously tuned from its commonly accepted value at 620 down to the 700 nm range, only attained previously by alloying Te into GaSe (GaSex Te1- x ). This is accomplished by manipulating various vdW epitaxy kinetic factors, which allows the choice bet ween screw-dislocation-driven and layer-bylayer growth, and the design of different morphologies with different material-substrate interaction (strain) energies.