Ultrafast many-body bright-dark exciton transition in anatase TiO2.

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors.

1D Electronic Flat Bands in Untwisted Moiré Superlattices.

After the preparation of 2D electronic flat band (EFB) in van der Waals (vdW) superlattices, recent measurements suggest the existence of 1D electronic flat bands (1D-EFBs) in twisted vdW bilayers. However, the realization of 1D-EFBs is experimentally elusive in untwisted 2D layers, which is desired considering their fabrication and scalability. Herein, the discovery of 1D-EFBs is reported in an untwisted in situ-grown two atomic-layer Bi(110) superlattice self-aligned on an SnSe(001) substrate using scanning probe microscopy measurements and density functional theory calculations. While the Bi-Bi dimers of Bi zigzag (ZZ) chains are buckled, the epitaxial lattice mismatch between the Bi and SnSe layers induces two 1D buckling reversal regions (BRRs) extending along the ZZ direction in each Bi(110)-11 × 11 supercell. A series of 1D-EFBs arises spatially following BRRs that isolate electronic states along the armchair (AC) direction and localize electrons in 1D extended states along ZZ due to quantum interference at a topological node. This work provides a generalized strategy for engineering 1D-EFBs in utilizing lattice mismatch between untwisted rectangular vdW layers.

Plasmonic topological quasiparticle on the nanometre and femtosecond scales.

At the interface of classical and quantum physics, the Maxwell and Schrödinger equations describe how optical fields drive and control electronic phenomena to enable lightwave electronics at terahertz or petahertz frequencies and on ultrasmall scales1-5. The electric field of light striking a metal interacts with electrons and generates light-matter quasiparticles, such as excitons6 or plasmons7, on an attosecond timescale. Here we create and image a quasiparticle of topological plasmonic spin texture in a structured silver film. The spin angular momentum components of linearly polarized light interacting with an Archimedean coupling structure with a designed geometric phase generate plasmonic waves with different orbital angular momenta. These plasmonic fields undergo spin-orbit interaction and their superposition generates an array of plasmonic vortices. Three of these vortices can form spin textures that carry non-trivial topological charge8 resembling magnetic meron quasiparticles9. These spin textures are localized within a half-wavelength of light, and exist on the timescale of the plasmonic field. We use ultrafast nonlinear coherent photoelectron microscopy to generate attosecond videos of the spatial evolution of the vortex fields; electromagnetic simulations and analytic theory confirm the presence of plasmonic meron quasiparticles. The quasiparticles form a chiral field, which breaks the time-reversal symmetry on a nanometre spatial scale and a 20-femtosecond timescale (the 'nano-femto scale'). This transient creation of non-trivial spin angular momentum topology pertains to cosmological structure creation and topological phase transitions in quantum matter10-12, and may transduce quantum information on the nano-femto scale13,14.

Ultrafast Photoemission Electron Microscopy: Imaging Plasmons in Space and Time.

Plasmonics is a rapidly growing field spanning research and applications across chemistry, physics, optics, energy harvesting, and medicine. Ultrafast photoemission electron microscopy (PEEM) has demonstrated unprecedented power in the characterization of surface plasmons and other electronic excitations, as it uniquely combines the requisite spatial and temporal resolution, making it ideally suited for 3D space and time coherent imaging of the dynamical plasmonic phenomena on the nanofemto scale. The ability to visualize plasmonic fields evolving at the local speed of light on subwavelength scale with optical phase resolution illuminates old phenomena and opens new directions for growth of plasmonics research. In this review, we guide the reader thorough experimental description of PEEM as a characterization tool for both surface plasmon polaritons and localized plasmons and summarize the exciting progress it has opened by the ultrafast imaging of plasmonic phenomena on the nanofemto scale.

Coherent multidimensional photoelectron spectroscopy of ultrafast quasiparticle dressing by light.

Depending on the applied strength, electromagnetic fields in electronic materials can induce dipole transitions between eigenstates or distort the Coulomb potentials that define them. Between the two regimes, they can also modify the electronic properties in more subtle ways when electron motion becomes governed by time and space-periodic potentials. The optical field introduces new virtual bands through Floquet engineering that under resonant conditions interacts strongly with the preexisting bands. Under such conditions the virtual bands can become real, and real ones become virtual as the optical fields and electronic band dispersions entangle the electronic response. We reveal optical dressing of electronic bands in a metal by exciting four-photon photoemission from the Cu(111) surface involving a three-photon resonant transition from the Shockley surface band to the first image potential band. Attosecond resolved interferometric scanning between identical pump-probe pulses and its Fourier analysis reveal how the optical field modifies the electronic properties of a solid through combined action of dipole excitation and field dressing.

Optical field tuning of localized plasmon modes in Ag microcrystals at the nanofemto scale.

Nanoscale plasmonic field enhancement at sub-wavelength metallic particles is crucial for surface sensitive spectroscopy, ultrafast microscopy, and nanoscale energy transduction. Here, we demonstrate control of the spatial distribution of localized surface plasmon modes at sub-optical-wavelength crystalline silver (Ag) micropyramids grown on a Si(001) surface. We employ multiphoton photoemission electron microscopy (mP-PEEM) to image how the plasmonic field distributions vary with the photon energy, light polarization, and phase in coherent two-pulse excitation. For photon energy hυ > 2.0 eV, the mP-PEEM images show single photoemission locus, which splits into a dipolar pattern that straddles the Ag crystal at a lower energy. We attribute the variation to the migration of plasmon resonances from the Ag/vacuum to the Ag/Si interfaces by choice of the photon energy. Furthermore, the dipolar response of the Ag/Si interface follows the polarization state of light: for linearly polarized excitations, the plasmon dipole follows the in-plane electric field vector, while for circularly polarized excitations, it tilts in the direction of the handedness due to the conversion of spin angular momentum of light into orbital angular momentum of the plasmons excited in the sample. Finally, we show the coherent control of the spatial plasmon distribution by exciting the sample with two identical circularly polarized light pulses with delay defined with attosecond precision. The near field distribution wobbles at the pyramid base as the pump-probe delay is advanced due to interferences among the contributing fields. We illustrate how the frequency, polarization, and pulse structure can be used to design and control plasmon fields on the nanofemto scale for applications in chemistry and physics.

Nonlinear Plasmonic Photoelectron Response of Ag(111).

Photons can excite collective and single-particle excitations in metals; the collective plasmonic excitations are of keen interest in physics, chemistry, optics, and nanotechnology because they enhance coupling of electromagnetic energy and can drive nonlinear processes in electronic materials, particularly where their dielectric function ϵ(ω) approaches zero. We investigate the nonlinear angle-resolved two-photon photoemission (2PP) spectroscopy of the Ag(111) surface through the ϵ(ω) near-zero region. In addition to the Einsteinian single-particle photoemission, the 2PP spectra report unequivocal signatures of nonlocal dielectric, plasmonically enhanced, excitation processes.

Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions.

Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C60 monolayer. Scanning tunneling microscopy reveals the C60 lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C60 and BP reduce the inter-C60 distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C60 acquires an effective mass of 0.53-0.70 me (me is the mass of free electrons), and has carrier mobility of ~200 to 440 cm2V-1s-1. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.

K Atom Promotion of O2 Chemisorption on Au(111) Surface.

Alkali atoms are known to promote or poison surface catalytic chemistry. To explore alkali promotion of catalysis and to characterize discharge species in alkali-oxygen batteries, we examine coadsorption of K and O2 on Au(111) surface at the atomic scale by scanning tunneling microscopy (STM) and density functional theory (DFT). On a clean Au(111) surface, O2 molecules may weakly physisorb, but when Au(111) is decorated with K+ ions, they chemisorb into structures that depend on the adsorbate concentrations and substrate templating. At low K coverages, an ordered quantum lattice of K2O2 complexes forms through intramolecular attractive and intermolecule repulsive interactions. For higher K and O2 coverages, the K2O2 complexes condense first into triangular islands, which further coalesce into rhombohedral islands, and ultimately into incommensurate films. No structures display internal contrast possibly because of high structural mutability. DFT calculations explain the alkali-promoted coadsorption in terms of three center, cation-π interactions where pairs of K+ coordinate the π-orbitals on each side of O2 molecules, and in addition O2 forms a covalent bond to Au(111) surface. The K promoted adsorption of O2 is catalyzed by charge transfer from K atoms to Au(111) substrate and ultimately to O2 molecules, forming O2-δ in a redox state between the peroxo and superoxo. Tunneling d I/d V spectra of K2O2 complexes exhibit inordinately intense inelastic progression involving excitation of the O-O stretching vibration, but absence of a Kondo effect suggests that the magnetic moment of O2 is quenched.

Coherent optical and acoustic phonons generated at lattice-matched GaP/Si(0 0 1) heterointerfaces.

Thin GaP films can be grown on an exact Si(0 0 1) substrate with nearly perfect lattice match. We perform all-optical pump-probe measurements to investigate the ultrafast electron-phonon coupling at the buried interface of GaP/Si. Above-bandgap excitation with a femtosecond laser pulse can induce coherent longitudinal optical (LO) phonons both in the GaP overlayer and in the Si substrate. The coupling of the GaP LO phonons with photoexcited plasma is reduced significantly with decreasing GaP layer thickness from 56 to 16 nm due to the quasi-two-dimensional confinement of the plasma. The same laser pulse can also generate coherent longitudinal acoustic phonons in the form of a strain pulse. The strain pulse induces not only a periodic modulation in the optical reflectivity as it propagates in the semiconductor, but also a sharp spike when it arrives at the GaP layer boundary. The acoustic pulse induced at the GaP/Si interface is remarkably stronger than that at the Si surface, suggesting a possible application of the GaP/Si heterostructure as an opto-acoustic transducer. The amplitude and the phase of the reflectivity modulation varies with the GaP layer thickness, which can be understood in terms of the interference caused by the multiple acoustic pulses generated at the top surface and at the buried interface.

Ultrafast Microscopy of Spin-Momentum-Locked Surface Plasmon Polaritons.

Using two-photon photoemission electron microscopy (2P-PEEM) we image the polarization dependence of coupling and propagation of surface plasmon polaritons (SPPs) launched from edges of a triangular, micrometer size, single-crystalline Ag crystal by linearly or circularly polarized light. 2P-PEEM records interferences between the optical excitation field and SPPs it creates with nanofemto space-time resolution. Both the linearly and circularly polarized femtosecond light pulses excite spatially asymmetric 2PP yield distributions, which are imaged. We attribute the asymmetry for linearly polarized light to the relative alignments of the laser polarization and triangle edges, which affect the efficiency of excitation of the longitudinal component of the SPP field. For circular polarization, the asymmetry is caused by matching of the spin angular momenta (SAM) of light and the transverse SAM of SPPs. Moreover, we show that the interference patterns recorded in the 2P-PEEM images are cast by phase shifts and amplitudes for coupling of light into the longitudinal and transverse components of SPP fields. While the interference patterns depend on the excitation polarization, nanofemto movies show that the phase and group velocities of SPPs are independent of SAM of light in time-reversal invariant media. Simulations of the wave interference reproduce the polarization and spin-dependent coupling of optical pulses into SPPs.

Coherent Electron Transfer at the Ag/Graphite Heterojunction Interface.

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Ultrafast Microscopy: Imaging Light with Photoelectrons on the Nano-Femto Scale.

Experimental methods for ultrafast microscopy are advancing rapidly. Promising methods combine ultrafast laser excitation with electron-based imaging or rely on super-resolution optical techniques to enable probing of matter on the nano-femto scale. Among several actively developed methods, ultrafast time-resolved photoemission electron microscopy provides several advantages, among which the foremost are that time resolution is limited only by the laser source and it is immediately capable of probing of coherent phenomena in solid-state materials and surfaces. Here we present recent progress in interference imaging of plasmonic phenomena in metal nanostructures enabled by combining a broadly tunable femtosecond laser excitation source with a low-energy electron microscope.

Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions.

Hot electron processes at metallic heterojunctions are central to optical-to-chemical or electrical energy transduction. Ultrafast nonlinear photoexcitation of graphite (Gr) has been shown to create hot thermalized electrons at temperatures corresponding to the solar photosphere in less than 25 fs. Plasmonic resonances in metallic nanoparticles are also known to efficiently generate hot electrons. Here we deposit Ag nanoclusters (NC) on Gr to study the ultrafast hot electron generation and dynamics in their plasmonic heterojunctions by means of time-resolved two-photon photoemission (2PP) spectroscopy. By tuning the wavelength of p-polarized femtosecond excitation pulses, we find an enhancement of 2PP yields by 2 orders of magnitude, which we attribute to excitation of a surface-normal Mie plasmon mode of Ag/Gr heterojunctions at 3.6 eV. The 2PP spectra include contributions from (i) coherent two-photon absorption of an occupied interface state (IFS) 0.2 eV below the Fermi level, which electronic structure calculations assign to chemisorption-induced charge transfer, and (ii) hot electrons in the π*-band of Gr, which are excited through the coherent screening response of the substrate. Ultrafast pump-probe measurements show that the IFS photoemission occurs via virtual intermediate states, whereas the characteristic lifetimes attribute the hot electrons to population of the π*-band of Gr via the plasmon dephasing. Our study directly probes the mechanisms for enhanced hot electron generation and decay in a model plasmonic heterojunction.

Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface.

Photogenerated charge carrier dynamics near molecule/TiO2 interfaces are important for the photocatalytic and photovoltaic processes. To understand this fundamental aspect, we performed a time-domain ab initio nonadiabatic molecular dynamics study of the photogenerated hole dynamics at the CH3OH/rutile TiO2(110) interface. We studied the forward and reverse hole transfer between TiO2 and CH3OH as well as the hole energy relaxation to the valence band maximum. First, we show that the hole-trapping ability of CH3OH depends strongly on the adsorption structure. Only when the CH3OH is deprotonated to form chemisorbed CH3O will ∼15% of the hole be trapped by the molecule. Second, we find that strong fluctuations of the HOMO energies of the adsorbed molecules induced by electron-phonon coupling provide additional channels, which accelerate the hole energy relaxation. Third, we demonstrate that the charge transfer and energy relaxation processes depend significantly on temperature. When the temperature decreases from 100 to 30 K, the forward hole transfer and energy relaxation processes are strongly suppressed because of the reduction of phonon occupation. These results indicate that the molecule/TiO2 energy level alignment, thermal excitation of a phonon, and electron-phonon coupling are the key factors that determine the photogenerated hole dynamics. Our studies provide valuable insights into the photogenerated charge and energy transfer dynamics at molecule/semiconductor interfaces.