Electron-Phonon Interactions in Transition Metal Oxides Studied by Resonance Raman Scattering

Sammanfattning: In this thesis, studies of strong electron-phonon interactions in a number of transition metal oxides are presented. Two different electron-phonon interaction mechanisms are identified; Franck-Condon scattering and infrared active longitudinal optical (IR LO) two-phonon activation. The main experimental technique used is temperature dependent resonance Raman scattering and the electron-phonon interactions are studied by the resonant effects they cause on the first and higher order Raman active phonon scattering. The mixed transition metal oxide LaFe$_{0.5}$Cr$_{0.5}$O$_{3}$ with orthorhombic perovskite structure has been studied in detail using resonance Raman scattering with incident photon energies between $hbaromega$=1.83 ($lambda$=676 nm) and $hbaromega$=4.13 eV ($lambda$=300 nm) and variable temperatures. It is established that the characteristic Franck-Condon multi-phonon scattering of a local oxygen breathing mode appears as the photon energy is tuned to the Fe-Cr charge transfer gaps. This interpretation is supported by results obtained from LaFe$_{1-x}$Cr$_{x}$O$_{3}$ (0$leq$x$leq$1) which show that the Franck-Condon resonance is critically sensitive to the presence of both Fe and Cr ions in the structure and by Sr-doping in La$_{1-x}$Sr$_{x}$Fe$_{0.5}$Cr$_{0.5}$O$_{3-delta}$ which shows that the Franck-Condon resonance is sensitive to local effects. In addition to the Franck-Condon effect, Fr"ohlich interaction induced IR LO two-phonon scattering is observed in the perovskites LaFeO$_{3}$ using $lambda$=515 nm ($hbaromega$=2.41 eV) and LaFe$_{0.5}$Cr$_{0.5}$O$_{3}$ using $lambda$=334 nm ($hbaromega$=3.71 eV). Interestingly, these different resonance effects can be made to mix either by an introduction of a small amount of Cr in LaFeO$_{3}$ or by incident photon energy tuning in LaFe$_{0.5}$Cr$_{0.5}$O$_{3}$ The results in the perovskites are complemented by observations in the spin ladder compound Sr$_{14}$Cu$_{24}$O$_{41}$ where an IR LO two-phonon resonance is activated for incident photon energies around the 1.8 eV charge transfer gap. In the spin ladder compound this resonance is linked to the formation of a charge density wave in the copper-oxide ladder layers below T=200 K. In combination, these observations illustrate the complexity of electron-phonon interactions in transition metal oxides and further establish resonance Raman scattering (in particular the higher order phonon scattering) as a sensitive probe of electron-phonon interactions and the relation between local and global effects in correlated material systems.

  Denna avhandling är EVENTUELLT nedladdningsbar som PDF. Kolla denna länk för att se om den går att ladda ner.