Browsing by Author "Gulde, Max"

Graphene-based nanostructured systems and van der Waals heterostructures comprise a material class of growing technological and scientific importance. Joining materials with vastly different properties, polymer/graphene heterosystems promise diverse applications in surface and nanotechnology, including photovoltaics or nanotribology. Fundamentally, molecular adsorbates are prototypical systems to study confinement-induced phase transitions exhibiting intricate dynamics, which require a comprehensive understanding of the dynamical and static properties on molecular time and length scales. Here, we investigate the dynamics and the structure of a single polyethylene chain on free-standing graphene by means of molecular dynamics simulations. In equilibrium, the adsorbed polymer is orientationally linked to the graphene as two-dimensional folded-chain crystallite or at elevated temperatures as a floating solid. The associated superstructure can be reversibly melted on a picosecond time scale upon quasi-instantaneous substrate heating, involving ultrafast heterogeneous melting via a transient floating phase. Our findings elucidate time-resolved molecular-scale ordering and disordering phenomena in individual polymers interacting with solids, yielding complementary information to collective friction and viscosity, and linking to recent experimental observables from ultrafast electron diffraction. We anticipate that the approach will help in resolving nonequilibrium phenomena of hybrid polymeric systems over a broad range of time and length scales.

Strong-field physics, an extreme limit of light-matter interaction(1-3), is expanding into the realm of surfaces(4,5) and nanostructures(6-11) from its origin in atomic and molecular science(12-15). The attraction of nanostructures lies in two intimately connected features: local intensity enhancement and sub-wavelength confinement of optical fields. Local intensity enhancement facilitates access to the strong-field regime and has already sparked various applications, whereas spatial localization has the potential to generate strong-field dynamics exclusive to nanostructures. However, the observation of features unattainable in gaseous media is challenged by many-body effects and material damage, which arise under intense illumination of dense systems(16-19). Here, we non-destructively access this regime in the solid state by employing single plasmonic nanotips and few-cycle mid-infrared pulses, making use of the wavelength-dependence of the interaction, that is, the ponderomotive energy. We investigate strong-field photoelectron emission and acceleration from single nanostructures over a broad spectral range, and find kinetic energies of hundreds of electronvolts. We observe the transition to a new regime in strong-field dynamics, in which the electrons escape the nanolocalized field within a fraction of an optical half-cycle. The transition into this regime, characterized by a spatial adiabaticity parameter, would require relativistic electrons in the absence of nanostructures. These results establish new degrees of freedom for the manipulation and control of electron dynamics on femtosecond and attosecond timescales, combining optical near-fields and nanoscopic sources.

We present strong-field photoemission from plasmonic nanotips driven by ultrashort pulses at wavelengths of 0.8-8μm, reaching Keldysh parameters down to 0.1. We identify a sub-cycle acceleration regime that is exclusive to confined fields in nanostructures.

The problem of highly nonlinear photoemission from a metal surface is considered using analytical and numerical approaches. Descriptions are found which cover both the weak-field and the strong-field regimes and the transition between them. The results of a time-dependent perturbation theory are in very good agreement with those from more numerically involved schemes, including a variational version of the Floquet method and a Crank-Nicolson-like numerical scheme. The implemented Crank-Nicolson variant uses transparent boundary conditions and an incident plane-wave state in the metal. Both numerical approaches give very similar results for weak and intermediate fields, while in the strong-field regime the Crank-Nicolson scheme is more effective than the Floquet method. We find an enhancement in the effective nonlinearity in the weak-field regime, which is caused by surface scattering of the final state. The presented theory also covers angular emission probabilities as a function of light intensity and explains an increase toward forward emission with growing field strength.

Nonlinear photoelectron emission from metallic nanotips is explored in the strong-field regime. The passage between the multiphoton and the optical field emission regimes is clearly identified. The experimental observations are in agreement with a quantum mechanical strong-field model.

Two-dimensional systems such as surfaces and molecular monolayers exhibit a multitude of intriguing phases and complex transitions. Ultrafast structural probing of such systems offers direct time-domain information on internal interactions and couplings to a substrate or bulk support. We have developed ultrafast low-energy electron diffraction and investigate in transmission the structural relaxation in a polymer/graphene bilayer system excited out of equilibrium. The laser-pump/electron-probe scheme resolves the ultrafast melting of a polymer superstructure consisting of folded-chain crystals registered to a free-standing graphene substrate. We extract the time scales of energy transfer across the bilayer interface, the loss of superstructure order, and the appearance of an amorphous phase with short-range correlations. The high surface sensitivity makes this experimental approach suitable for numerous problems in ultrafast surface science.