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We report experiments and calculations investigating the pressure and temperature dependences of the optical phonons in BaZrS 3 , and the pressure dependence of its absorption edge. BaZrS 3 is a chalcogenide perovskite in a novel class of materials being considered for photovoltaics. It is studied by Raman spectroscopy as functions of temperature (at 1 atm) and pressure (at 120K and 295K), and by pressure-transmission spectroscopy at 295K. Density functional theory (DFT) calculations predict the allowed Raman lines, their intensities, their pressure-shifts, and the band gap pressure-shift. Cooling shifts all but one of the phonon peaks to higher frequencies; the temperature coefficients are typical of semiconductors. A strong low-temperature peak at 392.3 cm-1 is attributed to resonant forbidden LO scattering; its shift with temperature has the opposite sign. The pressure coefficients of the phonon frequencies for all observed Raman peaks are positive, indicating no mode softening. The rates of pressure shift also are typical, and show the customary scaling with phonon frequency. Experiment and theory show good agreement on the pressureinduced frequency shifts. The BaZrS 3 absorption edge moves to lower energy with pressure, reflecting reduction of the band gap. The measured shift is ~ −0.015 eV/GPa, slightly less than the DFT result of −0.025 eV/GPa. We find no evidence that the perovskite structure of BaZrS 3 undergoes any phase changes under hydrostatic pressure to at least 8.9 GPa. Our results indicate the robust structural stability of BaZrS 3 , and suggest cation alloying as a viable approach for band gap engineering for photovoltaic and other applications.

Hydrostatic pressure can sometimes generate structural and chemical disorder within crystals. We review pressure-Raman experiments on ZnSe, ZnTe, and CdSe showing evidence for these phenomena. In ZnSe and ZnTe Raman spectra recorded with low laser flux show only pre-transition structural disorder on approaching the lowest pressure transition, as is typical for first-order phase changes. Spectra recorded with higher laser flux (sub-band-gap) observe precipitation of anion nanocrystals. This behavior is absent in CdSe. A model is developed that considers the role of crystal defects. The defects promote plastic deformation assisted by photoexcitation of Jahn–Teller distortions. Nanocrystals can precipitate on dislocations in deformed regions under energetically favorable conditions. Model calculations based on theories for precipitation in metals account for the influence of pressure on the nanocrystal formation in ZnSe and ZnTe, and explain its absence in CdSe. Material maps are constructed to predict the tendencies for similar precipitation in III–V, II–VI, I–VII, and chalcopyrite crystals.