Advancing time- and angle-resolved photoemission spectroscopy: The role of ultrafast laser development

In the last decade, there has been a proliferation of laser sources for time- and angle-resolved photoemission spectroscopy (TR-ARPES), building on the proven capability of this technique to tackle important scientific questions. In this review, we aim to identify the key motivations and technologies that spurred the development of various laser sources, from frequency up-conversion in nonlinear crystals to high-harmonic generation in gases. We begin with a historical overview of the field in Sec.1, framed by advancements in light source and electron spectrometer technology. An introduction to the fundamental aspects of the photoemission process and the observables that can be studied is given in Sec.2, along with its dependencies on the pump and probe pulse parameters. The technical aspects of TR-ARPES are discussed in Sec.3. Here, experimental limitations such as space charge and resultant trade-offs in source parameters are discussed. Details of various systems and their approach to these trade-offs are given in Sec.4. Within this discussion, we present a survey of TR-ARPES laser sources; a meta-analysis of these source parameters showcases the advancements and trends in modern systems. Lastly, we conclude with a brief discussion of future directions for TR-ARPES and its capabilities in elucidating equilibrium and non-equilibrium observables, as well as its integration with micro-ARPES and spin-resolved ARPES (Sec.5).Comment: 104 pages, 27 figure

Charge transfer state emission dynamics in blue-emitting functionalized silicon nanocrystals

We explore the dynamics of blue emission from dodecylamine and ammonia functionalized silicon nanocrystals (Si NCs) with average diameters of ∼3 and ∼6 nm using time-resolved photoluminescence (TRPL) spectroscopy. The Si NCs exhibit nanosecond PL decay dynamics that is independent of NC size and uniform across the emission spectrum. The TRPL measurements reveal complete quenching of core state emission by a charge transfer state that is responsible for the blue PL with a radiative recombination rate of ∼5 × 10^7 s^(−1). A detailed picture of the charge transfer state emission dynamics in these functionalized Si NCs is proposed

Terahertz Spectroscopy and Brewster Angle Reflection Imaging of Acoustic Tiles

A Brewster angle reflection imaging apparatus is demonstrated which is capable of detecting hidden water-filled voids in a rubber tile sample. This imaging application simulates a real-world hull inspection problem for Royal Canadian Navy Victoria-class submarines. The tile samples represent a challenging imaging application due to their large refractive index and absorption coefficient. With a rubber transmission window at approximately 80 GHz, terahertz (THz) sensing methods have shown promise for probing these structures in the laboratory. Operating at Brewster's angle allows for the typically strong front surface reflection to be minimized while also conveniently making the method insensitive to air-filled voids. Using a broadband THz time-domain waveform imaging system (THz-TDS), we demonstrate satisfactory imaging and detection of water-filled voids without complicated signal processing. Optical properties of the tile samples at low THz frequencies are also reported

Establishing non-thermal regimes in pump-probe electron-relaxation dynamics

Time- and angle-resolved photoemission spectroscopy (TR-ARPES) accesses the electronic structure of solids under optical excitation, and is a powerful technique for studying the coupling between electrons and collective modes. One approach to infer electron-boson coupling is through the relaxation dynamics of optically-excited electrons, and the characteristic timescales of energy redistribution. A common description of electron relaxation dynamics is through the effective electronic temperature. Such a description requires that thermodynamic quantities are well-defined, an assumption that is generally violated at early delays. Additionally, precise estimation of the non-thermal window -- within which effective temperature models may not be applied -- is challenging. We perform TR-ARPES on graphite and show that Boltzmann rate equations can be used to calculate the time-dependent electronic occupation function, and reproduce experimental features given by non-thermal electron occupation. Using this model, we define a quantitative measure of non-thermal electron occupation and use it to define distinct phases of electron relaxation in the fluence-delay phase space. More generally, this approach can be used to inform the non-thermal-to-thermal crossover in pump-probe experiments.Comment: 18 pages, 10 figure

Direct determination of mode-projected electron-phonon coupling in the time-domain

Ultrafast spectroscopies have become an important tool for elucidating the microscopic description and dynamical properties of quantum materials. In particular, by tracking the dynamics of non-thermal electrons, a material's dominant scattering processes -- and thus the many-body interactions between electrons and collective excitations -- can be revealed. Here we present a new method for extracting the electron-phonon coupling strength in the time domain, by means of time and angle-resolved photoemission spectroscopy (TR-ARPES). This method is demonstrated in graphite, where we investigate the dynamics of photo-injected electrons at the K point, detecting quantized energy-loss processes that correspond to the emission of strongly-coupled optical phonons. We show that the observed characteristic timescale for spectral-weight-transfer mediated by phonon-scattering processes allows for the direct quantitative extraction of electron-phonon matrix elements, for specific modes, and with unprecedented sensitivity.Comment: 19 pages, 4 figure

Nematicity dynamics in the charge-density-wave phase of a cuprate superconductor

Understanding the interplay between charge, nematic, and structural ordering tendencies in cuprate superconductors is critical to unraveling their complex phase diagram. Using pump-probe time-resolved resonant x-ray scattering on the (0 0 1) Bragg peak at the Cu L3 and oxygen K resonances, we investigate non-equilibrium dynamics of Qa = Qb = 0 nematic order and its association with both charge density wave (CDW) order and lattice dynamics in La1.65Eu0.2Sr0.15CuO4. In contrast to the slow lattice dynamics probed at the apical oxygen K resonance, fast nematicity dynamics are observed at the Cu L3 and planar oxygen K resonances. The temperature dependence of the nematicity dynamics is correlated with the onset of CDW order. These findings unambiguously indicate that the CDW phase, typically evidenced by translational symmetry breaking, includes a significant electronic nematic component.Comment: 16 pages, 4 figure

Fano interference of the Higgs mode in cuprate high-Tc superconductors

Despite decades of search for the pairing boson in cuprate high-Tc superconductors, its identity still remains debated to date. For this reason, spectroscopic signatures of electron-boson interactions in cuprates have always been a center of attention. For example, the kinks in the quasiparticle dispersion observed by angle-resolved photoemission spectroscopy (ARPES) studies have motivated a decade-long investigation of electron-phonon as well as electron-paramagnon interactions in cuprates. On the other hand, the overlap between the charge-order correlations and the pseudogap in the cuprate phase diagram has also generated discussions about the potential link between them. In the present study, we provide a fresh perspective on these intertwined interactions using the novel approach of Higgs spectroscopy, i.e. an investigation of the amplitude oscillations of the superconducting order parameter driven by a terahertz radiation. Uniquely for cuprates, we observe a Fano interference of its dynamically driven Higgs mode with another collective mode, which we reveal to be charge density wave fluctuations from an extensive doping- and magnetic field-dependent study. This finding is further corroborated by a mean field model in which we describe the microscopic mechanism underlying the interaction between the two orders. Our work demonstrates Higgs spectroscopy as a novel and powerful technique for investigating intertwined orders and microscopic processes in unconventional superconductors

Electron-phonon coupling in the time domain : TR-ARPES studies by a cavity-based XUV laser

The electron-phonon interaction is ubiquitous in crystalline materials, leaving fingerprints on both physical and electronic properties. In the study of materials, angle-resolved photoemission spectroscopy (ARPES) can uniquely access the electronic band structure, and the electron interactions encoded within. However, disentangling the contributions from different degrees of freedom -- such as electron-electron and electron-phonon – can be very challenging. Extension of ARPES into the time domain via pump-probe spectroscopy allows one to access the electronic structure on an ultrafast timescale: this is advantageous as the intertwined interactions in equilibrium become separated in the time domain. In this thesis, we use time-resolved (TR)-ARPES to study the electron-phonon interaction in graphite. Specifically, we observe spectral features arising from the photoexcitation of electrons from the valence band to the conduction band, followed by quantized energy-loss processes corresponding to the emission of strongly-coupled optical phonons. The transfer of spectral weight from an identifiable initial state to a final state is the direct manifestation of a microscopic two-body scattering process from which we can extract the mode-projected electron-phonon matrix element. The spectral features observed in this study arise from the non-thermal (i.e. non-Fermi-Dirac) occupation of electrons. We use Boltzmann simulations to map out various regimes in graphite where non-thermal features arise. These non-thermal signatures are not unique to graphite but are ubiquitous in pump-probe experiments and intrinsically tied to the dominant scattering processes, their timescales, and corresponding bottlenecks. Our results were made possible by a custom-built state-of-the-art laser source featuring cavity-enhanced high-harmonic generation. The source has three key features: First, high photon energies capable of mapping the whole Brillouin zone of materials; second, a high repetition rate that minimizes the space-charge effect; and last, a balanced time and energy resolution capable of studying subtle spectral features. All three elements were crucial in discerning the spectral features related to electron-phonon scattering in graphite, the first observation of its kind. With these results, we demonstrate that the maturation of high-harmonic sources can now offer a tunable table-top source with unprecedented intensity, repetition rate and resolution.Science, Faculty ofGraduat