Search

Two-dimensional transition metal dichalcogenides (TMDs) and organic semiconductors (OSCs) have emerged as promising material platforms for next-generation optoelectronic devices. The combination of both is predicted to yield emergent properties while retaining the advantages of their individual components. In OSCs the optoelectronic response is typically dominated by localized Frenkel-type excitons, whereas TMDs host delocalized Wannier-type excitons. However, much less is known about the spatial and electronic characteristics of excitons at hybrid TMD/OSC interfaces, which ultimately determine the possible energy and charge transfer mechanisms across the 2D-organic interface. Here, we use ultrafast momentum microscopy and many-body perturbation theory to elucidate a hybrid exciton at an TMD/OSC interface that forms via the ultrafast resonant F\"orster energy transfer process. We show that this hybrid exciton has both Frenkel- and Wannier-type contributions: Concomitant intra- and interlayer electron-hole transitions within the OSC layer and across the TMD/OSC interface, respectively, give rise to an exciton wavefunction with mixed Frenkel-Wannier character. By combining theory and experiment, our work provides previously inaccessible insights into the nature of hybrid excitons at TMD/OSC interfaces. It thus paves the way to a fundamental understanding of charge and energy transfer processes across 2D-organic heterostructures.

The vertical integration of multiple two-dimensional (2D) materials in heterostructures, held together by van der Waals forces, has opened unprecedented possibilities for modifying the (opto-)electronic properties of nanodevices. Graphene, with its remarkable opto-electronic properties, is an ideal candidate for such applications. Further candidates are 2D polymers, crystalline polymeric materials with customizable structure and electronic properties that can be synthesized in all mathematically possible Bravais lattices. In this study, we investigated the optoelectronic properties of a heterostructure created by pristine graphene and a rectangular 2D polyimide (2DPI) film. This imprints a new superlattice on graphene in conjunction with a direct influence on its electronic properties. Theoretical and experimental analyses reveal that interlayer charge exchange between the 2D polymer and graphene induces hole doping in the graphene layer. We have also observed that the properties of the heterostructure are dependent on the substrate used in experiments, likely due to the porous character of the 2DPI allowing direct interaction of graphene with the support. These findings highlight the unique ability to tailor functionalities in 2D polymers-based heterostructures, allowing the development of optoelectronic devices with precisely engineered properties and stimulating further exploration of the diverse phenomena accessible through tailored designs of the 2D polymers.

Recent advances in the field of condensed-matter physics have unlocked the potential to realize and control emergent material phases that do not exist in thermal equilibrium. One of the most promising concepts in this regard is Floquet engineering, the coherent dressing of matter via time-periodic perturbations. However, the broad applicability of Floquet engineering to quantum materials is still unclear. For the paradigmatic case of monolayer graphene, the theoretically predicted Floquet-induced effects, despite a seminal report of the light-induced anomalous Hall effect, have been put into question. Here, we overcome this problem by using electronic structure measurements to provide direct experimental evidence of Floquet engineering in graphene. We report light-matter-dressed Dirac bands by measuring the contribution of Floquet sidebands, Volkov sidebands, and their quantum path interference to graphene's photoemission spectral function. Our results finally demonstrate that Floquet engineering in graphene is possible, paving the way for the experimental realization of the many theoretical proposals on Floquet-engineered band structures and topological phases., Comment: 4 main figures, 3 extended figures

Excitons -- two-particle correlated electron-hole pairs -- are the dominant low-energy optical excitation in the broad class of semiconductor materials, which range from classical silicon to perovskites, and from two-dimensional to organic materials. Recently, the study of excitons has been brought on a new level of detail by the application of photoemission momentum microscopy -- a technique that has dramatically extended the experimental capabilities of time- and angle-resolved photoemission spectroscopy (trARPES). Here, we review how the energy- and momentum-resolved photoelectron detection scheme enables direct access to the energy landscape of bright and dark excitons, and, more generally, to the momentum-coordinate of the exciton that is fundamental to its wavefunction. Focusing on two-dimensional materials and organic semiconductors as two tuneable platforms for exciton physics, we first discuss the typical photoemission fingerprint of excitons in momentum microscopy and highlight that is is possible to obtain information not only on the electron- but also hole-component of the former exciton. Second, we focus on the recent application of photoemission orbital tomography to such excitons, and discuss how this provides a unique access to the real-space properties of the exciton wavefunction. Throughout the review, we detail how studies performed on two-dimensional transition metal dichalcogenides and organic semiconductors lead to very similar conclusions, and, in this manner, highlight the strength of time-resolved momentum microscopy for the study of optical excitations in semiconductors., Comment: review-article

The optical intersite spin transfer (OISTR) effect was recently verified in Fe$_{50}$Ni$_{50}$ using magneto-optical Kerr measurements in the extreme ultraviolet range. However, one of the main experimental signatures analyzed in this work, namely a magnetic moment increase at a specific energy in Ni, was subsequently found also in pure Ni, where no transfer from one element to another is possible. Hence, it is a much-discussed issue whether OISTR in FeNi alloys is real and whether it can be verified experimentally or not. Here, we present a comparative study of spin transfer in Fe$_{50}$Ni$_{50}$, Fe$_{19}$Ni$_{81}$ and pure Ni. We conclusively show that an increase in the magneto-optical signal is indeed insufficient to verify OISTR. However, we also show how an extended data analysis overcomes this problem and allows to unambiguously identify spin transfer effects. Concomitantly, our work solves the long-standing riddle about the origin of delayed demagnetization behavior of Ni in FeNi alloys.

The magneto-optical Kerr effect (MOKE) in the extreme ultraviolet (EUV) regime has helped to elucidate some of the key processes that lead to the manipulation of magnetism on ultrafast timescales. However, as we show in this paper, the recently introduced spectrally-resolved analysis of such data can lead to surprising experimental observations, which might cause misinterpretations. Therefore, an extended analysis of the EUV magneto-optics is necessary. Via experimental determination of the dielectric tensor, we find here that the non-equilibrium excitation in an ultrafast magnetization experiment can cause a rotation of the off-diagonal element of the dielectric tensor in the complex plane. In direct consequence, the commonly analyzed magneto-optic asymmetry may show time-dependent behaviour that is not directly connected to the magnetic properties of the sample. We showcase such critical observations for the case of ultrafast magnetization dynamics in Ni, and give guidelines for the future analysis of spectrally-resolved magneto-optical data and its comparison with theory.

The role and impact of spatial heterogeneity in two-dimensional quantum materials represents one of the major research quests regarding the future application of these materials in optoelectronics and quantum information science. In the case of transition-metal dichalcogenide heterostructures, in particular, direct access to heterogeneities in the dark-exciton landscape with nanometer spatial and ultrafast time resolution is highly desired, but remains largely elusive. Here, we introduce ultrafast dark field momentum microscopy to spatio-temporally resolve dark exciton formation dynamics in a twisted WSe$_2$/MoS$_2$ heterostructure with 55 femtosecond time- and 500~nm spatial resolution. This allows us to directly map spatial heterogeneity in the electronic and excitonic structure, and to correlate these with the dark exciton formation and relaxation dynamics. The benefits of simultaneous ultrafast nanoscale dark-field momentum microscopy and spectroscopy is groundbreaking for the present study, and opens the door to new types of experiments with unprecedented spectroscopic and spatiotemporal capabilities., Comment: 39 pages, 4 main figures, 8 supplemental figures

Van der Waals heterostructures show fascinating physics including trapped moire exciton states, anomalous moire exciton transport, generalized Wigner crystals, etc. Bilayers of transition metal dichalcogenides (TMDs) are characterized by long-lived spatially separated interlayer excitons. Provided a strong interlayer tunneling, hybrid exciton states consisting of interlayer and intralayer excitons can be formed. Here, electrons and/or holes are in a superposition of both layers. Although crucial for optics, dynamics, and transport, hybrid excitons are usually optically inactive and have therefore not been directly observed yet. Based on a microscopic and material-specific theory, we show that time- and angle-resolved photoemission spectroscopy (tr-ARPES) is the ideal technique to directly visualize these hybrid excitons. Concretely, we predict a characteristic double-peak ARPES signal arising from the hybridized hole in the MoS$_2$ homobilayer. The relative intensity is proportional to the quantum mixture of the two hybrid valence bands at the $\Gamma$ point. Due to the strong hybridization, the peak separation of more than 0.5 eV can be resolved in ARPES experiments. Our study provides a concrete recipe of how to directly visualize hybrid excitons and how to distinguish them from the usually observed regular excitonic signatures.

The energy landscape of optical excitations in mono- and few-layer transition metal dichalcogenides (TMDs) is dominated by optically bright and dark excitons. These excitons can be fully localized within a single TMD layer, or the electron- and the hole-component of the exciton can be charge-separated over multiple TMD layers. Such intra- or interlayer excitons have been characterized in detail using all-optical spectroscopies, and, more recently, photoemission spectroscopy. In addition, there are so-called hybrid excitons whose electron- and/or hole-component are delocalized over two or more TMD layers, and therefore provide a promising pathway to mediate charge-transfer processes across the TMD interface. Hence, an in-situ characterization of their energy landscape and dynamics is of vital interest. In this work, using femtosecond momentum microscopy combined with many-particle modeling, we quantitatively compare the dynamics of momentum-indirect intralayer excitons in monolayer WSe$_2$ with the dynamics of momentum-indirect hybrid excitons in heterobilayer WSe$_2$/MoS$_2$, and draw three key conclusions: First, we find that the energy of hybrid excitons is reduced when compared to excitons with pure intralayer character. Second, we show that the momentum-indirect intralayer and hybrid excitons are formed via exciton-phonon scattering from optically excited bright excitons. And third, we demonstrate that the efficiency for phonon absorption and emission processes in the mono- and the heterobilayer is strongly dependent on the energy alignment of the intralayer and hybrid excitons with respect to the optically excited bright exciton. Overall, our work provides microscopic insights into exciton dynamics in TMD mono- and bilayers., Comment: 27 pages, 5 figures

Excitons are two-particle correlated bound states that are formed due to Coulomb interaction between single-particle holes and electrons. In the solid-state, cooperative interactions with surrounding quasiparticles can strongly tailor the exciton properties and potentially even create new correlated states of matter. It is thus highly desirable to access such cooperative and correlated exciton behavior on a fundamental level. Here, we find that the ultrafast transfer of an exciton's hole across a type-II band-aligned moir\'e heterostructure leads to a surprising sub-200-fs upshift of the single-particle energy of the electron being photoemitted from the two-particle exciton state. While energy relaxation usually leads to an energetic downshift of the spectroscopic signature, we show that this unusual upshift is a clear fingerprint of the correlated interactions of the electron and hole parts of the exciton quasiparticle. In this way, time-resolved photoelectron spectroscopy is straightforwardly established as a powerful method to access exciton correlations and cooperative behavior in two-dimensional quantum materials. Our work highlights this new capability and motivates the future study of optically inaccessible correlated excitonic and electronic states in moir\'e heterostructures., Comment: 32 pages, 4 main figures, 5 supplemental figures

Harnessing the optoelectronic response of organic semiconductors requires a thorough understanding of the fundamental light-matter interaction that is dominated by the excitation of correlated electron-hole pairs, i.e. excitons. The nature of these excitons would be fully captured by knowing the quantum-mechanical wavefunction, which, however, is difficult to access both theoretically and experimentally. Here, we use femtosecond photoemission orbital tomography in combination with many-body perturbation theory to gain access to exciton wavefunctions in organic semiconductors. We find that the coherent sum of multiple electron-hole pair contributions that typically make up a single exciton can be experimentally evidenced by photoelectron spectroscopy. For the prototypical organic semiconductor buckminsterfullerene (C$_{60}$), we show how to disentangle such multiorbital contributions and thereby access key properties of the exciton wavefunctions including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics.

Moir\'e superlattices in atomically thin van-der-Waals heterostructures hold great promise for an extended control of electronic and valleytronic lifetimes, the confinement of excitons in artificial moir\'e lattices, and the formation of novel exotic quantum phases. Such moir\'e-induced emergent phenomena are particularly strong for interlayer excitons, where the hole and the electron are localized in different layers of the heterostructure. In order to exploit the full potential of correlated moir\'e and exciton physics, a thorough understanding of the ultrafast interlayer exciton formation process and the real-space wavefunction confinement in the moir\'e potential is indispensable. However, direct experimental access to these parameters is limited since most excitonic quasiparticles are optically dark. Here we show that femtosecond photoemission momentum microscopy provides quantitative access to these key properties of the moir\'e interlayer excitons. We find that interlayer excitons are dominantly formed on the sub-50~fs timescale via interlayer tunneling at the K valleys of the Brillouin zones. In addition, we directly measure energy-momentum fingerprints of the moir\'e interlayer excitons by mapping their spectral signatures within the mini Brillouin zone that is built up by the twisted heterostructure. From these momentum-fingerprints, we gain quantitative access to the modulation of the exciton wavefunction within the moir\'e potential in real-space. Our work provides the first direct access to the interlayer moir\'e exciton formation dynamics in space and time and reveals new opportunities to study correlated moir\'e and exciton physics for the future realization of exotic quantum phases of matter., Comment: 7 pages main text, 11 pages SI

We analyse recently measured nonlinear photoemission spectra from Ag surfaces that reveal resonances whose energies do not scale with the applied photon energy but stay pinned to multiples of bulk plasmon energy $\hbar\omega_p$ above the Fermi level. To elucidate these unexpected and peculiar features we investigate the spectra of plasmons generated in a solid by the optically pumped electronic polarization and their effect on photoemission. By combining quadratic response formalism for calculations of photoemission yield, a nonperturbative approach to inelastic electron scattering, and first-principles calculations for the electronic structure, we demonstrate the dependence of probability amplitude for single- and multiplasmon excitations on the basic parameters characterizing the photon pulse and the system. The resulting multiexcitation spectrum evolves towards a truncated plasmonic coherent state. Analogous concept is extrapolated to interpret plasmon generation by multiphoton excited electronic polarization. Based on this we elaborate a scenario that the thus created real plasmons act as supplementary frequency-locked pump field for non-Einsteinian plasmonically assisted channels of photoemission from metals. The established paradigm enables assignment and assessment of the observed linear $\hbar\omega_p$- and nonlinear $2\hbar\omega_p$-electron yields from Ag. Such effects may be exploited for selective filtering of optical energy conversion in electronic systems., Comment: Article as accepted for publication in Physical Review B

Auger scattering channels are of fundamental importance to describe and understand the non-equilibrium charge carrier dynamics in graphene. While impact excitation increases the number of carriers in the conduction band and has been observed experimentally, direct access to its inverse process, Auger recombination, has so far been elusive. Here, we tackle this problem by applying our novel setup for ultrafast time-resolved photoelectron momentum microscopy. Our approach gives simultaneous access to charge carrier dynamics at all energies and in-plane momenta within the linearly dispersive Dirac cones. We thus provide direct evidence for Auger recombination on a sub-10~fs timescale by identifying transient energy- and momentum-dependent populations far above the excitation energy. We compare our results with model calculations of scattering processes in the Dirac cone to support our experimental findings., Comment: 15 pages, paper and SI, 4+3 figures

Light-engineering of quantum materials via electromagnetic dressing is considered an on-demand approach for tailoring electronic band dispersions and even inducing topological phase transitions. For probing such dressed bands, photoemission spectroscopy is an ideal tool, and we employ here a novel experiment based on ultrafast photoemission momentum microscopy. Using this setup, we measure the in-plane momentum-dependent intensity fingerprints of the electromagnetically-dressed sidebands from a Au(111) surface for s- and p-polarized infrared driving. We find that at metal surfaces, due to screening of the driving laser, the contribution from Floquet-Bloch bands is negligible, and the dressed bands are dominated by the laser-assisted photoelectric effect. Also, we find that in contrast to general expectations, s-polarized light can dress free-electron states at large photoelectron momenta. Our results show that the dielectric response of the material must carefully be taken into account when using photoemission for the identification of light-engineered electronic band structures., Comment: 19 pages: 6 pages letter with 4 figures, 13 pages SI with 5 figures

We report a novel approach for coherent multi-photon photoemission band mapping of the entire Brillouin zone with infrared light that is readily implemented in a laboratory setting. We excite a solid state material, Ag(110), with intense femtosecond laser pulses to excite higher-order multi-photon photoemission; angle-resolved electron spectroscopic acquisition records photoemission at large in-plane momenta involving optical transitions from the occupied to unoccupied bands of the sample that otherwise might remain hidden by the photoemission horizon. We propose this as a complementary ultrafast method to time- and angle-resolved two-color, e.g. infrared pump and extreme ultraviolet probe, photoemission spectroscopy, with the advantage of being able to measure and control the coherent electron dynamics., Comment: 13 pages, 3 figures

Because silver has epsilon-near-zero (ENZ) in the near-UV spectral region, its optical response is expected to be dominantly plasmonic and nonperturbatively nonlinear. The ENZ properties of Ag have made it the material of choice for investigation of plasmonic optical effects in physics, chemistry, optics, and nanotechnology. We investigate the nonlinear angle-resolved two-photon photoemission (2PP) spectroscopy of Ag(111) surface in the ENZ region. In addition to the well-understood and documented spectroscopic features of Einsteinian photoemission involving dipole excitations of the single-particle occupied and unoccupied surface states, 2PP spectra possess other distinct features where the optical fields excite or are modified by the collective virtual and real plasmon excitations., Comment: 16 pages, 4 figures; 15 pages SI material, 6 figures

Light interacting with metals elicits an ultrafast coherent many-body screening response on sub- to few-femtosecond time-scales, which makes its experimental observation challenging. Here, we describe the coherent two-dimensional (2D) multi-photon photoemission study of the Shockley surface state (SS) of Ag(111) as a benchmark for spectroscopy of the coherent nonlinear response of metals to an optical field in the perturbative regime. Employing interferometrically time-resolved multi-photon photoemission spectroscopy (ITR-mPP), we correlate the coherent polarizations and populations excited in the sample with final photoelectron distributions where the interaction terminates. By measuring the non-resonant 3- and 4-photon photoemission of the SS state, as well as its replica structures in the above-threshold photoemission (ATP), we record the coherent response of the Ag(111) surface by 2D photoemission spectroscopy and relate it to its band structure. We interpret the mPP process by an optical Bloch equation (OBE) model, which reproduces the main features of the surface state coherent polarization dynamics recorded in ITR-mPP experiments: The spectroscopic components of the 2D photoelectron spectra are shown to depend on the nonlinear orders of the coherent photoemission process m as well as on the induced coherence n., Comment: 34 pages, 8 figures in main paper, pages 33 and 34: supplemental material, 1 figure

Controlled organic functionalization of silicon surfaces as integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, i.e., the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate which makes them effectively unreactive in competition with the direct pathway of cyclooctyne's strained triple bond., Comment: 16 pages, 5 figures, TOC figure