Advances in the accuracy and efficiency of first-principles electronic structure calculations have allowed detailed studies of the energetics of materials under high pressures. At the same time, improvements in the resolution of powder x-ray diffraction experiments and more sophisticated methods of data analysis have revealed the existence of many new and unexpected high-pressure phases. The most complete set of theoretical and experimental data obtained to date is for the group-IVA elements and the group-IIIA--VA and IIB--VIA compounds. Here the authors review the currently known structures and high-pressure behavior of these materials and the theoretical work that has been done on them. The capabilities of modern first-principles methods are illustrated by a full comparison with the experimental data.

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High-pressure phases of group-IV, III–V, and II–VI compounds

Silicon wafers subject to depth-sensing indentation tests have been studied using Raman microspectroscopy. We report a strong correlation between the shape of the load-displacement curve and the phase transformations occurring within a nanoindentation. The results of Raman microanalysis of nanoindentations in silicon suggest that sudden volume change in the unloading part of the load-displacement curve (“pop-out” or “kink-back” effect) corresponds to the formation of Si–XII and Si–III phases, whereas the gradual slope change of the unloading curve (“elbow”) is due to the amorphization of silicon on pressure release. The transformation pressures obtained in nanoindentation tests are in agreement with the results of high pressure cell experiments.

Effect of phase transformations on the shape of the unloading curve in the nanoindentation of silicon

Combining hardness indentation tests and micro-Raman spectroscopy it is shown that metallic Si-II is produced near the interface of a diamond indenter and silicon to a depth of about 0.5 μm, where the highest stresses (hydrostatic and deviatoric) exist. At fast unloading rates Si-II transforms to the amorphous state, whereas a mixture of the r8 high pressure polymorph Si-XII and the bc8 phase Si-III forms upon a slow load release. The region of Si-III+Si-XII is surrounded by the wurtzite structured Si-IV, where the stresses during the indentation had not been high enough to cause the transition to the metallic state. Thus, because of shear deformation a direct transformation to Si-IV takes place. Outside the phase-transformed regions the classical aspects of indentation-induced deformation by dislocation glide, twinning and crack formation are observed. Annealing of the high pressure phases leads to the formation of Si-IV at moderate temperatures and to the reversal to the original diamond structure (Si-I...

Phase transformations of silicon caused by contact loading

Group 14 elements (C, Si, and Ge) exist as various stable and metastable allotropes, some of which have been widely applied in industry. The discovery of new allotropes of these elements has long attracted considerable attention; however, the search is far from complete. Here we computationally discovered a tetragonal allotrope (12 atoms/cell, named T12) commonly found in C, Si, and Ge through a particle swarm structural search. The T12 structure employs sp3 bonding and contains extended helical six-membered rings interconnected by pairs of five- and seven-membered rings. This arrangement results in favorable thermodynamic conditions compared with most other experimentally or theoretically known sp3 species of group 14 elements. The T12 polymorph naturally accounts for the experimental d spacings and Raman spectra of synthesized metastable Ge and Si-XIII phases with long-puzzling unknown structures, respectively. We rationalized an alternative experimental route for the synthesis of the T12 phase via deco...

Tetragonal allotrope of group 14 elements.

During hardness indentation, materials are subjected to highly l highly localized stresses. These stresses not only cause crack formation and plastic deformation by dislocation gliding, but a complete change of the crystal structure and formation of amorphous phases or high-pressure polymorphs can occur in the zone of maximum contact stresses. Such contact-induced phase transformations were observed in hard and brittle materials including semiconductors (Si, Ge, GaAs and InSb) and common ceramic materials such as SiC and SiO2 (α-quartz and silica glass). A prime tool for their investigation is the Raman microspectroscopy of hardness indentations.



In Si and Ge, there is an initial transformation to metallic high-pressure phases upon hardness indentation and a subsequent formation of crystalline, nanocrystalline, or amorphous phases depending on the conditions of the hardness test, in particular the unloading rate. A phase transformation occurs also in InSb, whereas the results for GaAs do not give sufficient evidence for phase transformations. Indentation-induced amorphization has been observed in SiC and quartz. Even diamond has been shown to undergo amorphization and phase transformation under nonhydrostatic stress conditions imposed by indentation tests. Copyright © 1999 John Wiley & Sons, Ltd.

Fred Buehler

Papers

New metastable phases of silicon