Mode-Selective Control of the Crystal Lattice

Driving phase changes by selective optical excitation of specific vibrational modes in molecular and condensed phase systems has long been a grand goal for laser science. However, phase control has to date primarily been achieved by using coherent light fields generated by femtosecond pulsed lasers at near-infrared or visible wavelengths. This field is now being advanced by progress in generating intense femtosecond pulses in the mid-infrared, which can be tuned into resonance with infrared-active crystal lattice modes of a solid. Selective vibrational excitation is particularly interesting in complex oxides with strong electronic correlations, where even subtle modulations of the crystallographic structure can lead to colossal changes of the electronic and magnetic properties. In this Account, we summarize recent efforts to control the collective phase state in solids through mode-selective lattice excitation. The key aspect of the underlying physics is the nonlinear coupling of the resonantly driven phonon to other (Raman-active) modes due to lattice anharmonicities, theoretically discussed as ionic Raman scattering in the 1970s. Such nonlinear phononic excitation leads to rectification of a directly excited infrared-active mode and to a net displacement of the crystal along the coordinate of all anharmonically coupled modes. We present the theoretical basis and the experimental demonstration of this phenomenon, using femtosecond optical spectroscopy and ultrafast X-ray diffraction at a free electron laser. The observed nonlinear lattice dynamics is shown to drive electronic and magnetic phase transitions in many complex oxides, including insulator–metal transitions, charge/orbital order melting and magnetic switching in manganites. Furthermore, we show that the selective vibrational excitation can drive high-T_C cuprates into a transient structure with enhanced superconductivity. The combination of nonlinear phononics with ultrafast crystallography at X-ray free electron lasers may provide new design rules for the development of materials that exhibit these exotic behaviors also at equilibrium

Control of the electronic phase of a manganite by mode-selective vibrational excitation.

Controlling a phase of matter by coherently manipulating specific vibrational modes has long been an attractive (yet elusive) goal for ultrafast science. Solids with strongly correlated electrons, in which even subtle crystallographic distortions can result in colossal changes of the electronic and magnetic properties, could be directed between competing phases by such selective vibrational excitation. In this way, the dynamics of the electronic ground state of the system become accessible, and new insight into the underlying physics might be gained. Here we report the ultrafast switching of the electronic phase of a magnetoresistive manganite via direct excitation of a phonon mode at 71 meV (17 THz). A prompt, five-order-of-magnitude drop in resistivity is observed, associated with a non-equilibrium transition from the stable insulating phase to a metastable metallic phase. In contrast with light-induced and current-driven phase transitions, the vibrationally driven bandgap collapse observed here is not related to hot-carrier injection and is uniquely attributed to a large-amplitude Mn-O distortion. This corresponds to a perturbation of the perovskite-structure tolerance factor, which in turn controls the electronic bandwidth via inter-site orbital overlap. Phase control by coherent manipulation of selected metal-oxygen phonons should find extensive application in other complex solids--notably in copper oxide superconductors, in which the role of Cu-O vibrations on the electronic properties is currently controversial