The pressure dependence of thelo-to phonons in InAs has been investigated by Raman scattering using the diamond anvil cell. Indium arsenide transforms, presumably to the rock-salt structure at 70±1 kbar. The mode Grüneisen parameters for thelo-to phonons are γ_lo=0.99±0.03, γ_to=1.2±0.03 respectively. The effective charge,e*_T, for InAs decreases slightly with pressure and this trend is in accordance with the behaviour of other III–V zinc blende structured semiconductors: The structural phase transition is discussed in the light of theoretical calculations for phase stability of III–V compounds, as well as recent high pressure x-ray diffraction studies.

The pressure dependence of the vibrational modes in ZnP₂ has been investigated by Raman Spectroscopy using a diamond anvil cell, up to 150 kbar pressure. The intrachain phosphorus modes exhibit a strong pressure dependence whereas the low frequency Zn-P modes soften very slightly under pressure. For a crystal which is treated as a molecular crystal this is an unexpected result. It is suggested that the behaviour may be due to a buckling of the phosphorus chain, or due to a double bond promotion between P atoms, or a charge transfer under pressure. The shift in the energy gap has also been measured to 100 kbar hydrostatic pressure. There is a small initial blue shift which gradually changes over to a red shift. However the whole shift in 100 kbar is quite small. Combining the (dEg/dP)_T with the published (dEg/dT)_P the thermal expansion contribution and the electron-phonon interaction contribution were evaluated. The latter dominates the total (dEg/dT)_P of ZnP₂.

The effect of pressure on the 2H and 4H polytype of PbI₂ has been investigated by Raman and optical absorption spectroscopy, using the diamond anvil cell. The 2H-polytype undergoes pressure-induced phase transitions at 5 kbar and near 30 kbar. The 4H-polytype exhibits phase transitions near 8 kbar and above 30 kbar. The Raman modes abruptly change at these pressures. The optical absorption edge shifts red at the rate of 15±1 MeV/kbar in the 2H-PbI₂ and at the rate of 7 MeV/kbar in phase II. The latter phase is most likely to possess a 3d-structure and not a layer type. The possible structures for the high pressure phases are discussed.

The pressure dependence of the first-order Raman peak and two second-order Raman features of ThO₂ crystallizing in the fluorite-type structure is investigated using a diamond anvil cell, up to 40GPa. A phase transition from the fluorite phase is observed near 30 GPa as evidenced by the appearance of seven new Raman peaks. The high pressure phases of ThO₂ and CeO₂ exhibit similar Raman features and from this it is believed that the two structures are the same, and have the PbCl₂-type structure. The pressure dependence dω/dP of the observed phonons and their mode Grüneisen parameters are similar to the isostructural CeO₂. The observed second-order Raman features are also identified from the calculated phonon dispersion curves for ThO₂.

The pressure dependence of the direct and indirect bandgap of epitaxial In_0.52Al_0.48As on InP(001) substrate has been measured using photoluminescence up to 92 kbar hydrostatic pressure. The bandgap changes from Γ toX at an applied pressure of ∼ 43 kbar. Hydrostatic deformation potentials for both the Γ andX bandgaps are deduced, after correcting for the elastic constant (bulk modulus) mismatch between the epilayer and the substrate. For the epilayer we obtain$$(\Xi _d + \tfrac{1}{3}\Xi _u - a) as - (6 \cdot 92 + 0 \cdot 3) eV$$ and+(2.81±0.15)eV for the Γ andX bandgaps respectively. From the pressure dependence of the normalized Γ-bandgap photoluminescence intensity a Γ-X lifetime ratio, (τ_Γ/τ_X), of 4.1×10⁻³ is deduced.

Hydrostatic pressure has been used to tune in resonance Raman scattering (RRS) in bulk GaAs. Using a diamond anvil cell, both the photoluminescence peak (PL) and the 2 LO and LO-phonon Raman scattered intensities have been monitored, to establish RRS conditions. When theE₀ gap of GaAs matchesħω_S orħω_L, the 2 LO and LO-phonon intensity, respectively, exhibit resonance Raman scattering maxima, at pressures determined byħω_L. With 647.1 nm radiation (ħω_L = 1.916 eV), a sharp and narrow resonance peak at 3.75 GPa is observed for the 2 LO-phonon. At this pressure the 2 LO-phonon goes through its maximum intensity, and falls right on top of the PL peak, revealing thatħω_S(2 LO) =E₀. This is the condition for “outgoing” resonance. Experiments with other excitation energies (ħω_L) show, that the 2 LO resonance peak-pressure moves to higher pressure with increasingħω_L, and the shift follows precisely theE₀ gap. Thus, the 2 LO RRS is an excellent probe to follow theE₀ gap, far beyond the Γ-X cross-over point. A brief discussion of the theoretical expression for resonance Raman cross section is given, and from this the possibility of a double resonance condition for the observed 2 LO resonance is suggested. The LO-phonon resonance occurs at a pressure whenħω_L ≈E₀, but the pressure-induced transparency of the GaAs masks the true resonance profile.

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD₄⁴ symmetry toD₂⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.

High pressure Raman spectroscopic studies on Gd₂(MoO₄)₃(GMO) have been carried out at ambient temperature in the diamond cell to 10 GPa hydrostatic pressure. These experiments have revealed pressure-induced phase transitions in GMO near 2 GPa and 6.0 GPa. The first transition is from Pba2(β′) phase to another undetermined crystalline phase, designated as phase II, and the second transition is to an amorphized state. On releasing pressure there is a partial reversion to the crystalline state. The Raman data indicate that the amorphization is due to disordering of the MoO₄ tetrahedral units. Further, it is inferred from the nature of the Raman bands in the amorphized material that the Mo-O bond lengths and bond angles have a range of values, instead of a few set values. The results of the present study as well as previous high pressure-high temperature quenching experiments strongly support that pressure-induced amorphization in GMO is a consequence of the kinetically impededβ toα phase transition. The system in frustration becomes disordered. The rare earth trimolybdates crystallizing in theβ′ structure are all expected to undergo similar pressure-induced amorphization.

Raman and optical absorption studies under pressure have been conducted on KTb(MoO₄)₂ up to 35.5 GPa. A phase transformation occurs at 2.7 GPa when the crystal is pressurized at ambient temperature in a hydrostatic pressure medium. The sample changes to a deep yellow color at the transition and visibly contracts in theα-axis direction. The color shifts to red on further pressure increase. The Raman spectral features and the X-ray powder pattern change abruptly at the transition indicating a structural change. The pressure-induced transition appears to be a property of the layer-type alkali rare earth dimolybdates. However, the color change at the transition in KTb(MoO₄)₂ is rather unusual and is attributed to a valence change in Tb initiated by the structural transition and consequent intervalence charge transfer between Tb and Mo.In situ high pressure X-ray diffraction data suggest that phase II could be orthorhombic with a unit cell having 3 to 4% smaller volume than that of phase I.