A new class of insulating solids was recently discovered. Whenirradiated by a few visible photons, these solids give rise to amacroscopic excited domain that has new structural and electronicorders quite different from the starting ground state. This occurrenceis called photoinduced phase transition, and this multi-authoredbook reviews recent theoretical and experimental studies of this newphenomenon.
Ultrafast Phenomena XVI presents the latest advances in ultrafast science, including both ultrafast optical technology and the study of ultrafast phenomena. It covers picosecond, femtosecond and attosecond processes relevant to applications in physics, chemistry, biology, and engineering. Ultrafast technology has a profound impact in a wide range of applications, amongst them biomedical imaging, chemical dynamics, frequency standards, material processing, and ultrahigh speed communications. This book summarizes the results presented at the 16th International Conference on Ultrafast Phenomena and provides an up-to-date view of this important and rapidly advancing field.
Single-shot femtosecond spectroscopy was developed to study irreversible processes and materials far from equilibrium. It was then applied to investigate photoinduced phase transitions in semimetals and manganites. The dual-echelon single-shot instrument was developed, and noise sources, experimental artifacts, and the fundamental limits of the single-shot technique were explored. In this thesis, advances in the single-shot technique that allow for more detailed investigation of material processes and characterization of far-from-equilibrium dynamics in a wider range of systems are discussed. Experiments and modeling of photoinduced phase transitions in two classes of systems, semimetals and manganites, are presented. Both systems show collective structural change under photoexcitation that ultimately results in a low-symmetry to high-symmetry phase transition. In semimetals, the high symmetry phase relaxes after a few picoseconds, and in manganites, the higher symmetry phase persists essentially indefinitely. A photoinduced structural phase transition in bismuth is discussed in terms of the removal of a Peierls distortion by electronic excitation. When more than 2% of the valence electrons are excited, the Peierls distortion is inverted and the bismuth crystal is collectively driven into a symmetric crystalline phase. An extended two-temperature model is used to interpret and identify a photoinduced symmetric phase that exists above the damage threshold at low temperature and high excitation density. Analogous experiments and analysis on antimony and tellurium are discussed, demonstrating the generality of this method to exploring phase transitions in Peierls-distorted systems. A recently discovered photoinduced insulator-to-metal phase transition in epitaxially strained La2/3Ca1/3MnO3 on an NdGaO3 (001) substrate at low temperature is characterized by frequency-domain and time-domain spectroscopy. The ground state and metastable photoinduced phase in LCMO are characterized by their steady-state behavior. Conventional pump-probe and single-shot experiments are interpreted in terms of an eective medium model that describes the density of charge transfer excitations in the material. An extended two-parameter Ginzburg-Landau model with biquadratic coupling describes the ground state of the manganite phase diagram and the stability of the photoinduced metallic phase.
The main purpose of this Ph. D. thesis is to study the photo-induced transformations by a laser pulse in molecular materials. The results have been obtained thanks the use of pump-probe optical techniques. This required innovative experimental developments, including first attempts with a single shot technique. In the spincrosover family of molecular materials, in which light may induce the switching from a non magnetic to a magnetic state, for the first time we followed the transformation dynamics over ten decades in time scale, from 100 femtoseconds to a millisecond. It reveals that the process follows a complex pathway from molecular to material scale through a sequence of steps. A charge transfer organic compound, which exhibits an insulatior-to-metal phase transition, has also been investigated. A dynamics implying several coherent optical phonon modes has been clearly observed. The behaviour as a function of laser pulse intensity and temperature shows that the state photo-induced from the insulating phase differs from the metallic phase at thermal equilibrium. The newly developed single shot set-up proved able of recording changes upon an irreversible transformation, for instance inside a hysteresis regime. This set has been tested by observing photo-induced damages of a thin gold layer.
The discovery and control of new phases of matter are a central endeavor in materials research. Phase transition in two-dimensional (2D) materials has been achieved through laser irradiation, strain engineering, electrostatic doping, and controlled chemical vapor deposition growth, and laser irradiation is considered as a fast and clean technique for triggering phase transition. By using first-principles calculations, we predict that the monolayer MoTe2 exhibits a photo-induced phase transition (PIPT) from the semiconducting 2H phase to the topological 1T,Ä≤ phase. The purely electronic excitations by photon soften multiple lattice vibrational modes and lead to structural symmetry breaking within sub-picosecond timescales, which is shorter than the timescale of a thermally driven phase transition, enabling a controllable phase transition by means of photons. This finding provides deep insight into the underlying physics of the phase transition in 2D transition-metal ditellurides and show an ultrafast phase-transition mechanism for manipulation of the topological properties of 2D systems. More importantly, our finding opens a new avenue to discover the new families of PIPT materials that are very limited at present but are essential to design the next generation of devices operated at ultrafast speed.
Single-shot femtosecond spectroscopy has been developed and employed for the study of phase transitions of solid-state materials. Using two crossed echelons, a two dimensional spatial delay gradient was generated across a single probe pulse profile. This novel scheme enables us to monitor irreversible change in solids by acquiring many time-resolved data points with a single laser pulse. With the integration with a non-collinear optical parametric amplifier (NOPA) and a conventional pump-probe instrument, ultrafast dynamics of coherent lattice vibrations and photo-induced phase transitions were examined in two different systems. Ultrafast dynamics such as coherent lattice vibrations and bond softening were investigated for Bi thin films and bulk single crystals. Depending on the thickness, transient reflectivity was changed significantly. The variations are ascribed to different electronic structures possibly originating from quantum confinement. Bond softening exhibits a strong thickness dependence due to hot carrier dynamics as well as to the different electronic structures. At high pump fluences, no phonon oscillations were observed suggesting a phase transition to liquid or to a higher symmetry crystalline phase (reverse Peierls distortion). Together with thermal modeling, double pump measurements reveal nonthermal melting occurring in bulk and thin Bi films. A higher threshold fluence for nonthermal melting is observed in bulk bismuth as compared to thin films, suggesting ultrafast carrier dynamics such as ballistic transport. In addition to nonthermal effects, thermal effects such as inelastic electron-phonon scattering and nonradiative recombination play a crucial role in melting and cooling at later times after nonthermal melting takes place. A quasi one-dimensional platinum iodide complex showed strong oscillations in reflectivity which are attributed to oscillatory motions of wave packets on a selftrapped exciton (STE) potential surface., As optical excitation increased, electron transfer from Pt 2+ to an adjacent Pt4+ occurred over a wider range of lattice sites and weakened the oscillations. Above a certain pump fluence, oscillations disappeared completely indicating that the mixed valence, charge density wave state changed to monovalent, Mott-Hubbard phase. The reverse phase transition, i.e., from the MottHubbard phase to the charge density wave state began within 3 ps of the optical pump.
