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Structural changes at the semiconductor-insulator phase transition in the single layered La0.5Sr1.5MnO4 perovskite

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 Publication date 2011
  fields Physics
and research's language is English




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The semiconductor-insulator phase transition of the single-layer manganite La0.5Sr1.5MnO4 has been studied by means of high resolution synchrotron x-ray powder diffraction and resonant x-ray scattering at the Mn K edge. We conclude that a concomitant structural transition from tetragonal I4/mmm to orthorhombic Cmcm phases drives this electronic transition. A detailed symmetry-mode analysis reveals that condensation of three soft modes -Delta_2(B2u), X1+(B2u) and X1+(A)- acting on the oxygen atoms accounts for the structural transformation. The Delta_2 mode leads to a pseudo Jahn-Teller distortion (in the orthorhombic bc-plane only) on one Mn site (Mn1) whereas the two X1+ modes produce an overall contraction of the other Mn site (Mn2) and expansion of the Mn1 one. The X1+ modes are responsible for the tetragonal superlattice (1/2,1/2,0)-type reflections in agreement with a checkerboard ordering of two different Mn sites. A strong enhancement of the scattered intensity has been observed for these superlattice reflections close to the Mn K edge, which could be ascribed to some degree of charge disproportion between the two Mn sites of about 0.15 electrons. We also found that the local geometrical anisotropy of the Mn1 atoms and its ordering originated by the condensed Delta_2 mode alone perfectly explains the resonant scattering of forbidden (1/4,1/4,0)-type reflections without invoking any orbital ordering.

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We report the first observation of `orbital truncation rods -- the scattering arising from the termination of bulk orbital order at the surface of a crystal. The x-ray measurements, performed on a cleaved, single-layered perovskite, La0.5Sr1.5MnO4, reveal that while the crystallographic surface is atomically smooth, the orbital `surface is much rougher, with an r.m.s. deviation from the average `surface of ~0.7nm. The temperature dependence of this scattering shows evidence of a surface-induced second order transition.
We present a study of the effect of very high pressure on the orthorhombic perovskite GdMnO3 by Raman spectroscopy and synchrotron x-ray diffraction up to 53.2 GPa. The experimental results yield a structural and insulator-to-metal phase transition close to 50 GPa, from an orthorhombic to a metrically cubic structure. The phase transition is of first order with a pressure hysteresis of about 6 GPa. The observed behavior under very high pressure might well be a general feature in rare-earth manganites.
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