Diamond is an attractive material due to its extreme hardness, high thermal conductivity, quantum optical, and biomedical applications. There is still much that is not understood about how diamonds form, particularly at room temperature and without catalysts. In this work, a new route for the formation of nanocrystalline diamond and the diamond‐like phase lonsdaleite is presented. Both diamond phases are found to form together within bands with a core‐shell structure following the high pressure treatment of a glassy carbon precursor at room temperature. The crystallographic arrangements of the diamond phases revealed that shear is the driving force for their formation and growth. This study gives new understanding of how shear can lead to crystallization in materials and helps elucidate how diamonds can form on Earth, in meteorite impacts and on other planets. Finally, the new shear induced formation mechanism works at room temperature, a key finding that may enable diamond and other technically important nanomaterials to be synthesized more readily.
Glassy carbon (GC) is usually considered the prototypical super-elastic material, which can almost fully recover its shape after compression of several gigapascals (GPa). In this work, nanoindentation is used to study the mechanical response of GC, which was subjected to a range of high pressures using a diamond anvil cell (DAC). We show that GC starts to lose its elasticity after compression to 6 GPa and becomes clearly mechanically anisotropic after being compressed beyond ∼30 GPa. Molecular dynamics (MD) simulations are used to calculate Young's modulus before and after compression. Through our experimental results and MD simulations, we show that the elasticity of GC is at a minimum around 30 GPa but recovers after compression to higher pressures along the DAC compression axis.
Lonsdaleite is a hexagonal allotrope of carbon found in nature in meteorites and at meteorite impact sites. It has been predicted to have an indentation hardness greater than cubic diamond by first principles calculations. However, this has not been demonstrated experimentally. Here, nanoindentation was used to measure the hardness of two different lonsdaleite samples. One contains nanocrystalline lonsdaleite synthesized by high pressure compression of glassy carbon. The other is from a ureilite meteorite that contains lonsdaleite crystals up to [Formula: see text]1 [Formula: see text]m. The hardness of these two samples was determined using both the Oliver–Pharr and Meyer methods. Our results show that the hardness of the lonsdaleite samples is similar to that of diamond; therefore, there is no evidence that these forms of polycrystalline lonsdaleite are significantly harder than similar forms of diamond.
Germanium–tin (GeSn) alloys at sufficiently high Sn concentration, above several atomic percent, are the only group IV semiconductor exhibiting a direct bandgap and have generated much recent interest for optoelectronic applications into the mid-infrared region. Because the large lattice mismatch between GeSn and Si results in considerable strain for thin layers and a high defect density for thicker strain-relaxed layers, most reported GeSn growths incorporate a Ge buffer layer rather than depositing directly on Si substrates. Published reports of GeSn growth directly on Si utilize specialized precursors such as higher order germanes (Ge2H6, Ge3H8, or Ge4H10) or SnD4. In this paper, we report GeSn films with up to 10.6% Sn grown directly on Si substrates by remote plasma-enhanced chemical vapor deposition using GeH4 and SnCl4 precursors. These alloys have been characterized in detail using x-ray diffraction (XRD), transmission electron microscopy (TEM), and Rutherford backscattering spectrometry with channeling (RBS-C), as well as Raman spectroscopy (RS) and optical microscopy. The films studied are almost fully relaxed, with small residual strain observed, particularly in thinner films, and contain a high interface density of misfit dislocations that increases with Sn concentration. The defect density decreases toward the surface. Good agreement is found between the various characterization methods for the Sn content (XRD and RBS-C), lattice parameter measurement (XRD and TEM), and defect characterization (RBS-C, TEM, and RS). Such characterization of GeSn grown directly on Si substrates is essential to allow growth parameters to be optimized for the realization of the attractive optoelectronic properties of these alloys.
In article number 2004695, Dougal McCulloch and co‐workers report the synthesis of nanocrystalline diamond from a compressed graphitic precursor at room temperature in a diamond anvil cell. Diamond is one of the most important materials for 21st century technology, but there is much that is still not understood about how it forms. This article shows how the presence of shear at high pressures leads to the formation of both regular cubic diamond and hexagonal diamond (Lonsdaleite) without heating.
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