arXiv subjects

Klaus Kuhnke

Publications and source records attributed to Klaus Kuhnke.

13 recordsLinked to original sources

arXiv2026

Tuning single-molecule fluorescence by atomic-scale control of the local environment

Molecules that absorb and emit light play a central role in microscopy, light-emitting devices and photosynthesis. Their fluorescence arises from well-defined radiative transitions that are governed by the electronic states and their coupling to the nuclear motion that are influenced by the local environment. Yet the effect of controlled atomic-scale variations in the emitter surroundings remains unexplored. Here, we use scanning tunneling microscopy combined with optical spectroscopy to investigate the optical response of a single phthalocyanine to the change in the position of a nearby molecule, controlled with precision better than 100 pm. Upon decreasing the intermolecular distance, the molecular emission energy redshifts and its line profile evolves. Supported by theoretical calculations, we disentangle the electronic and nuclear contributions to the changes in fluorescence. We find that the redshift originates from the interaction between the excitations of the two molecules, while the lineshape changes reflect modifications of the molecular rotational degree of freedom and non-equilibrium dynamics. We extend this control to larger assemblies, where one molecule tunes the energies of two chromophores, mimicking the environmental tuning in photosynthetic systems. Our study provides atomic-scale insight into how the local environment affects the optical properties of molecular systems.

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arXiv2026

Probing up-conversion electroluminescence of decoupled porphyrin molecules in a plasmonic nanocavity

Molecular triplet states can produce significant phosphorescence and act as a relay state for luminescence, such as in up-conversion processes. While this property makes triplet emitters interesting for organic light-emitting diodes (OLEDs), the study of their luminescence at the single molecule level in high resolution scanning tunneling microscopy (STM) is challenging. We investigate individual Pd-octaethylporphyrin (PdOEP) molecules decoupled from Ag(100) and Ag(111) by an ultrathin NaCl layer and observe singlet and triplet emission lines at visible wavelengths, only about 100 nm apart from each other. This is in stark contrast to the metal or free-base phthalocyanines, for which typically the lowest triplet transitions lie in the far red or infrared where the sensitivity of charge coupled device (CCD) detectors decrease significantly. The singlet S1 state of PdOEP emits photons even when the photon energy is higher than the energy provided by a tunneling electron, in an energy up-conversion process. This mechanism requires a relay (or shelving) state in which energy is stored in the molecule for the interval between tunneling electrons. Analyzing the energy levels of different molecular states (S1, D0, and T1 states) and fitting the current dependencies of S1 under up-conversion electroluminescence (UCEL) condition for S1 and T1 emission, we verify the validity of a triplet-mediated up-conversion model.

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arXiv2025

Single-molecule phosphorescence and intersystem crossing in a coupled exciton-plasmon system

Scanning the sharp metal tip of a scanning tunneling microscope (STM) over a molecule allows tuning the coupling between the tip plasmon and a molecular fluorescence emitter. This allows access to local variations of fluorescence field enhancement and wavelength shifts, which are central parameters for characterizing the plasmon-exciton coupling. Performing the same for phosphorescence with molecular scale resolution remains a significant challenge. In this study, we present the investigation of phosphorescence from isolated Pt-Phthalocyanine molecules by analyzing tip-enhanced emission spectra in both current-induced and laser-induced phosphorescence. The latter directly monitors singlet-to-triplet state intersystem crossing of a molecule below the tip. The study contributes to a detailed understanding of triplet excitation pathways and their potential control at sub-molecular length scales. Additionally, the coupling of organic phosphors to plasmonic structures is a promising route for improving light-emitting diodes.

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arXiv2024

Scanning Tunneling Microscopy for Molecules: Effects of Electron Propagation into Vacuum

Using scanning tunneling microscopy (STM), we experimentally and theoretically investigate isolated platinum phthalocyanine (PtPc) molecules adsorbed on atomically thin NaCl(100) vapor deposited on Au(111). We obtain good agreement between theory and constant-height STM topography. We examine why strong distortions of STM images occur as a function of distance between molecule and STM tip. The images of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) exhibit, for increasing distance, significant radial expansion due to electron propagation in the vacuum. Additionally, the imaged angular dependence is substantially distorted. The LUMO image has substantial intensity along the molecular diagonals where PtPc has no atoms. In the electronic transport gap the image differs drastically from HOMO and LUMO, even at energies very close to these orbitals. As the tunneling becomes increasingly off-resonant, the eight angular lobes of the HOMO or of the degenerate LUMOs diminish and reveal four lobes with maxima along the molecular axes, where both, HOMO and LUMO have little or no weight. These images are strongly influenced by low-lying PtPc orbitals that have simple angular structures.

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arXiv2023

Character of electronic states in the transport gap of molecules on surfaces

We report on scanning tunneling microscopy (STM) topographs of individual metal phthalocyanines (MPc) on a thin salt (NaCl) film on a gold substrate, at tunneling energies within the molecule's electronic transport gap. Theoretical models of increasing complexity are discussed. The calculations for MPcs adsorbed on a thin NaCl layer on Au(111) demonstrate that the STM pattern rotates with the molecule's orientations - in excellent agreement with the experimental data. Thus, even the STM topography obtained for energies in the transport gap represent the structure of a one atom thick molecule. It is shown that the electronic states inside the transport gap can be rather accurately approximated by linear combinations of bound molecular orbitals (MOs). The gap states include not only the frontier orbitals but also surprisingly large contributions from energetically much lower MOs. These results will be essential for understanding processes, such as exciton creation, which can be induced by electrons tunneling through the transport gap of a molecule.

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arXiv2023

Anionic Character of the Conduction Band of Sodium Chloride

The alkali halides are ionic compounds. Each alkali atom donates an electron to a halogen atom, leading to ions with full shells. The valence band is mainly located on halogen atoms, while, in a traditional picture, the conduction band is mainly located on alkali atoms. Scanning tunnelling microscopy of NaCl at 4 K actually shows that the conduction band is located on Cl$^-$ because the strong Madelung potential reverses the order of the Na$^+$ 3s and Cl$^-$ 4s levels. We verify this reversal is true for both atomically thin and bulk NaCl, and discuss implications for II-VI and I-VII compounds.

cond-mat.mtrl-sci↗

arXiv2021

Atomic-scale structural fluctuations of a plasmonic cavity

We study fluctuations in plasmonic electroluminescence at the single-atom limit profiting from the precision of a low-temperature scanning tunneling microscope. First, we investigate the influence of a controlled single-atom transfer on the plasmonic properties of the junction. Next, we form a well-defined atomic contact of several quanta of conductance. In contact, we observe changes of the electroluminescence intensity that can be assigned to spontaneous modifications of electronic conductance, plasmonic excitation and optical antenna properties all originating from minute atomic rearrangements at or near the contact. The observations are relevant for the understanding of processes leading to spontaneous intensity variations in plasmon-enhanced atomic-scale spectroscopies.

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arXiv2020

Gigahertz frame rate imaging of charge-injection dynamics in a molecular light source

Light sources on the scale of single molecules can be addressed and characterized on their proper sub-nanometer scale by scanning tunneling microscopy induced luminescence (STML). Such a source can be driven by defined short charge pulses while the luminescence is detected with sub-nanosecond resolution. We introduce an approach to concurrently image the molecular emitter, which is based on an individual defect, with its local environment along with its luminescence dynamics at a resolution of a billion frames per second. The observed dynamics can be assigned to the single electron capture occurring in the low-nanosecond regime. While the emitter's location on the surface remains fixed, the scanning of the tip modifies the energy landscape for charge injection to the defect. The principle of measurement is extendable to fundamental processes beyond charge transfer like exciton diffusion.

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arXiv2019

Single Photon Emission from a Plasmonic Light Source Driven by a Local Field-Induced Coulomb Blockade

A hallmark of quantum control is the ability to manipulate quantum emission at the nanoscale. Through scanning tunneling microscopy induced luminescence (STML) we are able to generate plasmonic light originating from inelastic tunneling processes that occur in a few-nanometer thick molecular film of C$_{60}$ deposited on Ag(111). Single photon emission, not of excitonic origin, occurs with a 1/$e$ lifetime of a tenth of a nanosecond or less, as shown through Hanbury Brown and Twiss photon intensity interferometry. We have performed tight-binding calculations of the electronic structure for the combined Ag-C$_{60}$-tip system and obtained good agreement with experiment. The tunneling happens through electric field induced split-off states below the C$_{60}$ LUMO band, which leads to a Coulomb blockade effect and single photon emission. The use of split-off states is shown to be a general technique that has special relevance for narrowband materials with a large bandgap.

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arXiv2018

A single hydrogen molecule as an intensity chopper in an electrically-driven plasmonic nanocavity

Photon statistics is a powerful tool for characterizing the emission dynamics of nanoscopic systems and their photophysics. Recent advances that combine correlation spectroscopy with scanning tunneling microscopy-induced luminescence (STML) have allowed measuring the emission dynamics from individual molecules and defects demonstrating their nature as single photon emitters. The application of correlation spectroscopy to the analysis of the dynamics of a well-characterized adsorbate system in ultrahigh vacuum remained to be shown. Here we combine single photon time correlations with STML to measure the dynamics of individual $H_2$ molecules between a gold tip and a Au(111) surface. An adsorbed $H_2$ molecule performs recurrent excursions below the tip apex. We use the fact that the presence of the $H_2$ molecule in the junction modifies plasmon emission to study the adsorbate dynamics. Using the $H_2$ molecule as a chopper for STM-induced optical emission intensity we demonstrate bunching in the plasmonic photon train in a single measurement over six orders of magnitude in the time domain (from microseconds to seconds) that takes only a few seconds. Our findings illustrate the power of using photon statistics to measure the diffusion dynamics of adsorbates with STML.

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arXiv2018

Photon super-bunching from a generic tunnel junction

Generating correlated photon pairs at the nanoscale is a prerequisite to creating highly integrated optoelectronic circuits that perform quantum computing tasks based on heralded single-photons. Here we demonstrate fulfilling this requirement with a generic tip-surface metal junction. When the junction is luminescing under DC bias, inelastic tunneling events of single electrons produce a photon stream in the visible spectrum whose super-bunching index is 17 when measured with a 53 picosecond instrumental resolution limit. These photon bunches contain true photon pairs of plasmonic origin, distinct from accidental photon coincidences. The effect is electrically rather than optically driven - completely absent are pulsed lasers, down-conversions, and four-wave mixing schemes. This discovery has immediate and profound implications for quantum optics and cryptography, notwithstanding its fundamental importance to basic science and its ushering in of heralded photon experiments on the nanometer scale.

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arXiv2018

Single charge and exciton dynamics probed by molecular-scale-induced electroluminescence

Excitons and their constituent charge carriers play the central role in electroluminescence mechanisms determining the ultimate performance of organic optoelectronic devices. The involved processes and their dynamics are often studied with time-resolved techniques limited by spatial averaging that obscures the properties of individual electron-hole pairs. Here we overcome this limit and characterize single charge and exciton dynamics at the nanoscale by using time-resolved scanning tunnelling microscopy-induced luminescence (TR-STML) stimulated with nanosecond voltage pulses. We use isolated defects in C$_{60}$ thin films as a model system into which we inject single charges and investigate the formation dynamics of a single exciton. Tuneable hole and electron injection rates are obtained from a kinetic model that reproduces the measured electroluminescent transients. These findings demonstrate that TR-STML can track dynamics at the quantum limit of single charge injection and can be extended to other systems and materials important for nanophotonic devices.

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arXiv2005

Growth and surface alloying of Fe on Pt(997)

The growth of ultra-thin layers of Fe on the vicinal Pt(997) surface is studied by thermal energy He atom scattering (TEAS) and Auger electron spectroscopy (AES) in the temperature range between 175K and 800K. We find three distinct regimes of qualitatively different growth type: Below 450K the formation of a smooth first monolayer, at and above 600K the onset of bulk alloy formation, and at intermediate temperature 500K - 550K the formation of a surface alloy. Monatomic Fe rows are observed to decorate the substrate steps between 175K and 500K. The importance of the high step density is discussed with respect to the promotion of smooth layer growth and with respect to the alloying process and its kinetics.

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