arXiv subjects

Anna Rosławska

Publications and source records attributed to Anna Rosławska.

14 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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arXiv2024

Gating single-molecule fluorescence with electrons

Tip-enhanced photoluminescence (TEPL) measurements are performed with sub-nanometer spatial resolution on individual molecules decoupled from a metallic substrate by a thin NaCl layer. TEPL spectra reveal progressive fluorescence quenching with decreasing tip-molecule distance when electrons tunneling from the tip of a scanning tunneling microscope are injected at resonance with the molecular states. Rate equations based on a many-body model reveal that the luminescence quenching is due to a progressive population inversion between the ground neutral (S$_0$) and the ground charge ($D_0^-$) states of the molecule occurring when the current is raised. We demonstrate that both the bias voltage and the atomic-scale lateral position of the tip can be used to gate the molecular emission. Our approach can in principle be applied to any molecular system, providing unprecedented control over the fluorescence of a single molecule.

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arXiv2024

Electrically driven cascaded photon-emission in a single molecule

Controlling electrically-stimulated quantum light sources (QLS) is key for developing integrated and low-scale quantum devices. The mechanisms leading to quantum emission are complex, as a large number of electronic states of the system impacts the emission dynamics. Here, we use a scanning tunneling microscope (STM) to excite a model QLS, namely a single molecule. The luminescence spectra reveal two lines, associated to the emission of the neutral and positively charged molecule, both exhibiting single-photon source behavior. In addition, we find a correlation between the charged and neutral molecule's emission, the signature of a photon cascade. By adjusting the charging/discharging rate, we can control these emission statistics. This generic strategy is further established by a rate equation model revealing the complex internal dynamics of the molecular junction.

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arXiv2023

Submolecular-scale control of phototautomerization

Many natural and artificial reactions including photosynthesis or photopolymerization are initiated by stimulating organic molecules into an excited state, which enables new reaction paths. Controlling light-matter interaction can influence this key concept of photochemistry, however, it remained a challenge to apply this strategy to control photochemical reactions at the atomic scale. Here, we profit from the extreme confinement of the electromagnetic field at the apex of a scanning tunneling microscope (STM) tip to drive and control the rate of a free-base phthalocyanine phototautomerization with submolecular precision. By tuning the laser excitation wavelength and choosing the STM tip position, we control the phototautomerization rate and the relative tautomer population. This sub-molecular optical control can be used to study any other photochemical processes.

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arXiv2022

Tip-induced excitonic luminescence nanoscopy of an atomically-resolved van der Waals heterostructure

Low-temperature scanning tunneling microscopy is used to probe, with atomic-scale spatial resolution, the intrinsic luminescence of a van der Waals heterostructure, made of a transition metal dichalcogenide monolayer stacked onto a few-layer graphene flake supported by an Au(111) substrate. Sharp emission lines arising from neutral, charged and localised excitons are reported. Their intensities and emission energies vary as a function of the nanoscale environment of the van der Waals heterostructure, explaining the variability of the emission properties observed with diffraction-limited approaches. Our work paves the way towards understanding and control of optoelectronic phenomena in moiré superlattices with atomic-scale resolution.

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arXiv2021

Internal Stark effect of single-molecule fluorescence

The optical properties of chromophores can be efficiently tuned by electrostatic fields generated in their close environment, a phenomenon that plays a central role for the optimization of complex functions within living organisms where it is known as internal Stark effect (ISE). Here, we realised an ISE experiment at the lowest possible scale, by monitoring the Stark shift generated by charges confined within a single chromophore on its emission energy. To this end, a scanning tunneling microscope (STM) functioning at cryogenic temperatures is used to sequentially remove the two central protons of a free-base phthalocyanine chromophore deposited on a NaCl-covered Ag(111) surface. STM-induced fluorescence measurements reveal spectral shifts that are associated to the electrostatic field generated by the internal charges remaining in the chromophores upon deprotonation.

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arXiv2021

Energy funnelling within multichromophore architectures monitored with subnanometre resolution

In natural and artificial light-harvesting complexes (LHC) the resonant energy transfer (RET) between chromophores enables an efficient and directional transport of solar energy between collection and reaction centers. The detailed mechanisms involved in this energy funneling are intensely debated, essentially because they rely on a succession of individual RET steps that can hardly be addressed separately. Here, we developed a scanning tunnelling microscopy-induced luminescence (STML) approach allowing visualizing, addressing and manipulating energy funneling within multi-chromophoric structures with sub-molecular precision. We first rationalize the efficiency of the RET process at the level of chromophore dimers. We then use highly resolved fluorescence microscopy (HRFM) maps to follow energy transfer paths along an artificial trimer of descending excitonic energies which reveals a cascaded RET from high- to low-energy gap molecules. Mimicking strategies developed by photosynthetic systems, this experiment demonstrates that intermediate gap molecules can be used as efficient ancillary units to convey energy between distant donor and acceptor chromophores. Eventually, we demonstrate that the RET between donors and acceptors is enhanced by the insertion of passive molecules acting as non-covalent RET bridges. This mechanism, that occurs in experiments performed in inhomogeneous media and which plays a decisive role in fastening RET in photosynthetic systems, is reported at the level of individual chromophores with atomic-scale resolution. As it relies on organic chromophores as elementary components, our approach constitutes a powerful model to address fundamental physical processes at play in natural LHC.

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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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