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.

/pdf/high-pressure-phases-of-group-iv-iii-v-and-ii-vi-compounds-4wptdc31z8.pdf

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

The currently known structures and properties of group?IV elements and III-V compounds at high pressure are reviewed. Structural properties of various phases, as determined by experimental techniques, predominantly x-ray crystallography using diamond anvil cells, are covered first. The relative equilibrium stability of these phases, as determined by theoretical methods, is also discussed. Metastable phases and the processing techniques by which they can be made are examined, introducing the importance of phase transition kinetics in determining what is actually seen. Elastic and vibrational properties are then considered, looking at how elastic constants and phonon frequencies are affected by increasing pressure and how this can help us to understand the phase diagram and transition kinetics. Finally, using these ideas, it is shown how one can formulate equilibrium pressure-temperature equations of state for these materials. Throughout, the review draws on both experimental and theoretical work, and emphasizes features which seem to be generic to these tetrahedral semiconductors and their high-pressure phases.

http://iopscience.iop.org/article/10.1088/0034-4885/64/4/202/pdf

High-pressure phases of group IV and III-V semiconductors

Publisher Summary This chapter discusses structural transitions in the group IV, III–V, and II–VI semiconductors under pressure. The most preferred technique of structural transitions is energy-dispersive diffraction (EDX) in which the full white beam of the synchrotron falls on the sample. The diffraction pattern is recorded as a function of X-ray energy at a fixed scattering angle. The resolution of EDX powder patterns is limited to that of the solid-state detector. The patterns are unavoidably contaminated with fluorescence lines from the sample. The tight collimation of the diffracted beam required to define the scattering angle often leads to poor-powder averaging with the effect that peak intensities are unreliable—for example, the ability to detect and characterize sample microstructure effects, which are known to cause serious problems in high-pressure work. Preferred orientation (PO) can alter peak intensities dramatically leading to a strong reflection that is apparently absent from a powder pattern.

Chapter 3 Structural Transitions in the Group IV, III-V, and II-VI Semiconductors under Pressure

A systematic study of the II-VI, II-V, and group-IV semiconductors using angle-dispersive diffraction techniques is revealing new structures and transitions that significantly modify the accepted structural systematics of these materials. Recent new results from Ge, ZnSe, InSb, and GaAs extend the range of some aspects already indicated by our previous work, and new intermediate phases have been found in InSb, and in HgSe and HgTe.

New Structural Systematics in the II–VI, III–V, and Group-IV Semiconductors at High Pressure

Nonexistence of the diatomic beta -tin structure

Using angle-dispersive diffraction techniques and synchrotron radiation, we have made a detailed re-examination of the high-pressure behaviour of a number of core II-VI, III-V and group IV semiconductors. Despite much previous work on these materials, the good resolution afforded by angle-dispersive techniques, and the high-sensitivity of the image-plate area detector have yielded many new results which reveal that the accepted structural systematics have to be modified quite substantially. In this paper, we summarise the newly emerging structural systematics, and use the results to show how access to full 2-d powder patterns has proved essential in determining correct crystal structures.

2-d data collection in high pressure powder diffraction studies-applications to semiconductors

Structural studies of III–V and group IV semiconductors at high pressure

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2-d data collection in high pressure powder diffraction studies-applications to semiconductors

Structural studies of III–V and group IV semiconductors at high pressure