Search

Novel phases of Si that are predicted to have industrially desirable properties can be recovered after indentation-induced pressure. However, the thermal stability of these phases is not well understood. Furthermore, in the past, different methods of annealing have resulted in conflicting reports on annealing stability and transformation pathways. This study investigates the thermal stability of several metastable Si phases called r8-Si, bc8-Si, hd-Si, and Si-XIII under furnace annealing, incremental annealing, and laser annealing using Raman microspectroscopy and electron diffraction. The temperature range of stability for these metastable phases is thus determined. Of particular interest, hd-Si is stable to a much higher temperature than previously reported, being the predominant phase observed in this study after annealing at 450 °C. This finding was enabled through a new method for confirming the presence of hd-Si by detailed electron diffraction. This high thermal stability generates renewed interest in exploiting this phase for industrial applications, such as strain-tailored solar absorption. [ABSTRACT FROM AUTHOR]

The phase behavior of carbon at high pressure and the search for carbon structures denser than diamond has been explored for decades showing large discrepancies, with many fundamental questions remaining unresolved. Here we show evidence of melting above the graphite-diamond-liquid (GDL) triple point (∼13 GPa, 4000 K) up to 50 GPa on samples recovered from single flash-heating events using spectroscopic and electron microscopic methods. The results show that for all pressures, diamond melts below the triple point temperature contradicting previous studies, most of which predict a positive slope of the melting curve. [ABSTRACT FROM AUTHOR]

Exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursor materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3±0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44±0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications. [ABSTRACT FROM AUTHOR]

The Paris-Edinburgh press is a widely available, highly adaptable pressure cell commonly used while collecting neutron scattering data. Here, we detail the use of the VX3 and VX5 Paris-Edinburgh presses on the Wide-Angle Neutron Diffractometer (WAND 2 ) at the High Flux Isotope Reactor at Oak Ridge National Laboratory. We first give a detailed overview of the instrument setup and alignment capabilities used at WAND 2 . We then demonstrate the high pressure capabilities through three examples. The first example focuses on diffraction data obtained from a lithium-diamond mixture to 10 GPa with the use of single toroidal cubic boron nitride anvils. Other examples include the room temperature compressions of germanium (up to 16 GPa) and the mineral malachite with double toroidal sintered diamond anvils. This work thereby represents the first studies above 10 GPa at the High Flux Isotope Reactor and opens the door for future user experiments at these elevated pressures. [ABSTRACT FROM AUTHOR]

The transformation of diamond-cubic silicon to the metallic β-Sn phase is known to be "sluggish," even when the critical pressure (∼11 GPa) for the transformation is reached. In this letter, we use nanoindentation to apply pressures to just above the critical threshold. In this regime, the sample displays purely elastic behavior at zero hold time. As the hold time at maximum load is increased up to 180 s, the percentage of indents that plastically deform also increase. Interestingly, the indents deform via one of two distinct processes: either via a phase transformation to a mixed bc8/r8-Si end phase, or by initiation of crystalline defects. Raman spectroscopy and cross-sectional transmission electron microscopy are used to show that the two deformation mechanisms are mutually exclusive under the indentation conditions presented here, and elastic modelling was utilized to propose a model for this mutually exclusive behavior. Hence, this behavior enhances the potential for application of the exotic bc8/r8-Si end phase. [ABSTRACT FROM AUTHOR]

This study uses high-temperature nanoindentation coupled with in situ electrical measurements to investigate the temperature dependence (25-200 °C) of the phase transformation behavior of diamond cubic (dc) silicon at the nanoscale. Along with in situ indentation and electrical data, ex situ characterizations, such as Raman and cross-sectional transmission electron microscopy, have been used to reveal the indentation-induced deformation mechanisms. We find that phase transformation and defect propagation within the crystal lattice are not mutually exclusive deformation processes at elevated temperature. Both can occur at temperatures up to 150 °C but to different extents, depending on the temperature and loading conditions. For nanoindentation, we observe that phase transformation is dominant below 100 °C but that deformation by twinning along {111} planes dominates at 150 °C and 200 °C. This work, therefore, provides clear insight into the temperature dependent deformation mechanisms in dc-Si at the nanoscale and helps to clarify previous inconsistencies in the literature. [ABSTRACT FROM AUTHOR]

Nanoindentation-induced phase transformations have been studied in amorphous Ge thin films. These films initially tend to deform via plastic flow of the amorphous phase under load but at a critical pressure a sudden phase transformation occurs. This transformation, to a soft metallic (β-Sn-like)-Ge phase confined under the indenter, is signified by a "pop-in" event on loading. Following "pop-in," the indentation tests fall into two distinct types of behavior. In one case, the rate of deformation with increasing load after "pop-in" increases, and the observed end-phase following complete unloading is observed to be predominately diamond-cubic Ge. In the other case, the deformation rate (slope of the loading curve) remains the same as that before "pop-in," and the end phases following unloading are found to contain predominantly unstable r8 and more stable hexagonal Ge phases. The different transformation pathways for these two cases are shown to be related to the probability that the soft (β-Sn-like)-Ge phase volume, which suddenly forms at the transformation pressure, is either unconstrained by the indenter tip (the first case) or totally constrained under the indenter tip (in the latter case). [ABSTRACT FROM AUTHOR]

High temperature nanoindentation has been performed on pure ion-implanted amorphous silicon (unrelaxed a-Si) and structurally relaxed a-Si to investigate the temperature dependence of mechanical deformation, including pressure-induced phase transformations. Along with the indentation load-depth curves, ex situ measurements such as Raman micro-spectroscopy and crosssectional transmission electron microscopy analysis on the residual indents reveal the mode of deformation under the indenter. While unrelaxed a-Si deforms entirely via plastic flow up to 200 °C, a clear transition in the mode of deformation is observed in relaxed a-Si with increasing temperature. Up to 100 °C, pressure-induced phase transformation and the observation of either crystalline (r8/bc8) end phases or pressure-induced a-Si occurs in relaxed a-Si. However, with further increase of temperature, plastic flow rather than phase transformation is the dominant mode of deformation. It is believed that the elevated temperature and pressure together induce bond softening and "defect" formation in structurally relaxed a-Si, leading to the inhibition of phase transformation due to pressure-releasing plastic flow under the indenter. [ABSTRACT FROM AUTHOR]

Thermally induced phase transformation of Si-III/Si-XII zones formed by nanoindentation has been studied during low temperature (200

The effect of the local oxygen concentration in ion-implanted amorphous Si (a-Si) on nanoindentation-induced phase transformations has been investigated. Implantation of oxygen into the a-Si films has been used to controllably introduce an approximately constant concentration of oxygen, ranging from ∼1018 to ∼1021 cm-3, over the depth range of the phase transformed zones. Nanoindentation was performed under conditions that ensure a phase transformed zone composed completely of Si-III/XII in the nominally oxygen-free a-Si. The effect of the local oxygen concentration has been investigated by analysis of the unloading curves, Raman microspectroscopy, and cross-sectional transmission electron microscopy (XTEM). The formation of Si-III/XII is suppressed with increasing oxygen concentration, favoring a greater volume of a-Si within the zones. The Raman microspectroscopy and XTEM verify that the volume of Si-III/XII decreases with increasing O concentration. With the smaller volumes of Si-III/XII, the pop-out normally observed on load versus penetration depth curves during unloading decreases in magnitude, becoming more kinklike and is barely discernable at high concentrations of oxygen. The probability of forming any high pressure phases is reduced from 1 to ∼0.1 for a concentration of 1021 cm-3. We suggest that the bonding of O with Si reduces the formation of Si-III/XII during unloading through a similar mechanism to that of oxygen-retarded solid phase crystallization of a-Si. [ABSTRACT FROM AUTHOR]

The deformation behavior of ion-implanted (unrelaxed) and annealed ion-implanted (relaxed) amorphous silicon (a-Si) under spherical indentation at room temperature has been investigated. It has been found that the mode of deformation depends critically on both the preparation of the amorphous film and the scale of the mechanical deformation. Ex situ measurements, such as Raman microspectroscopy and cross-sectional transmission electron microscopy, as well as in situ electrical measurements reveal the occurrence of phase transformations in all relaxed a-Si films. The preferred deformation mode of unrelaxed a-Si is plastic flow, only under certain high load conditions can this state of a-Si be forced to transform. In situ electrical measurements have revealed more detail of the transformation process during both loading and unloading. We have used ELASTICA simulations to obtain estimates of the depth of the metallic phase as a function of load, and good agreement is found with the experiment. On unloading, a clear change in electrical conductivity is observed to correlate with a “pop-out” event on load versus penetration curves. [ABSTRACT FROM AUTHOR]