arXiv subjects

Sebastian Hammer

Publications and source records attributed to Sebastian Hammer.

12 recordsLinked to original sources

arXiv2026

Prospects for Direct Electron Detectors in Ultrafast Electron Diffraction and Scattering Experiments

Ultrafast electron diffraction and phonon-diffuse scattering [UED(S)] experiments make use of photo-induced changes to electron scattering intensity across 2D detectors to report on a very wide range of dynamic structural phenomena in molecules and materials. Hybrid pixel counting detectors (HPCDs) are a promising technology for improved sensitivity and signal-to-noise in UED(S) experiments, as they offer near-zero readout noise and dark counts with the possibility of new acquisition modalities (e.g., shot-to-shot normalization) due to their high frame rates. However, it is well known that HPCDs suffer from count losses at high electron fluxes even in CW beam applications. How this translates to ultrashort electron pulse exposures has yet to be determined and is critical to understanding the application of this technology to ultrafast electron scattering experiments. Here we show that count losses are significantly exacerbated in ultrafast (pulsed) experiments and that HPCDs require unconventional data handling and saturate above $\approx\!2$ electrons per pixel per pulse. This count-rate limitation presents a severe constraint on electron bunch charge when interrogating single crystal samples. Normalization strategies to optimize signal-to-noise in UED(S) and a complete model for measurement uncertainties using HPCDs are developed and tested using a large dataset. Finally, we suggest ways HPCDs could be better adapted to ultrashort pulsed beam experiments.

physics.ins-det↗

arXiv2025

Competing excitonic couplings as origin of mimicked phase transitions in zinc-phthalocyanine single crystals

The optical properties of molecular crystals are largely determined by the excitonic coupling of neighboring molecules. This coupling is extremely sensitive to the arrangement of adjacent molecular units, as their electronic interaction is defined by the relative orientation of the individual transition dipole moments and their wave function overlap. Hence, the optical properties, such as fluorescence, are usually highly anisotropic and good indicators of structural changes during the variation of intensive thermodynamic parameters like temperature or pressure. Here, we discuss the peculiar though archetypical case of $\beta$-phase zinc-phthalocyanine: In single crystals, we report a sudden change of spectral emission with temperature from a broad, unpolarized Frenkel-exciton type luminescence to a narrow, highly polarized superradiance-like fluorescence below 80 K. Surprisingly, we find that there is no sign of a discrete structural phase transition in this temperature regime. To understand this apparent contradiction, we perform polarization-, temperature- and time-dependent photoluminescence measurements along different crystallographic directions to fully map the emission characteristics of the crystal-exciton. By means of ab-initio calculations on a density functional theory level we conclude that our observations are consistent with a dimer exciton model when considering thermalized electronic states. As such, our study presents a representative case study on a well-established molecular material class demonstrating that caution is advised when attributing discrete changes in electronic observables to a structural phase transition. As we show for zinc-phthalocyanine in its $\beta$-phase modification, slowly varying excitonic couplings and thermal redistribution of excitations can mimic the same signatures attributed to a structural phase transition.

cond-mat.mtrl-sci↗

arXiv2025

Unveiling the Role of Solvents in DBTTF:HATCN Ternary Cocrystals

Donor-acceptor (D:A) cocrystals offer a promising platform for next-generation optoelectronic applications, but the impact of residual solvent molecules on their properties remains an open question. We investigate six novel D:A cocrystals of dibenzotetrathiafulvalene (DBTTF) and 1,4,5,8,9,11-hexaazatriphenylenehexacarbo-nitrile (HATCN), prepared via solvent evaporation, yielding 1:1 molar ratios, and horizontal vapor deposition, resulting in solvent-free 3:2 cocrystals. Combining spectroscopy and density-functional theory (DFT) calculations, we find that, while the electronic and optical properties of the cocrystals are largely unaffected by solvent inclusion, the charge transfer mechanism is surprisingly complex. Raman spectroscopy reveals a consistent charge transfer of 0.11 $e$ across all considered structures, corroborated by DFT calculations on solvent-free systems. Partial charge analysis reveals that in solvated cocrystals, solvent molecules actively participate in the charge transfer process as primary electron acceptors. This involvement can perturb the expected D:A behavior, revealing a faceted charge-transfer mechanism in HATCN even beyond the established involvement of its cyano group. Overall, our study demonstrates that while solution-based methods preserve the intrinsic D:A characteristics, solvents can be leveraged as active electronic components, opening new avenues for material design.

cond-mat.mtrl-sci↗

arXiv2025

How to Fix Silver for Plasmonics

Silver (Ag) is considered an ideal material for plasmonic applications in the visible wavelength regime due to its superior optical properties, but its use is limited by the poor chemical stability and structural quality of thermally evaporated thin films and resulting nanostructures. In this study, we present a simple approach to enhance the structural and optical quality as well as the chemical stability of Ag thin films by alloying with gold (Au) through thermal co-evaporation. We investigate Ag$_{100-x}$Au$_x$ thin films with Au contents ranging from 5 to 20 at% analyzing their surface morphology, crystallite structure, optical properties, and chemical stability. Our results show that low Au concentrations significantly reduce the roughness of co-evaporated thin films (down to 0.4 nm RMS), and significantly enhance the resistance to oxidation, while maintaining a defined crystallite growth. Importantly, these improvements are achieved without the need for template stripping, metallic wetting layers, or epitaxial substrates, enabling direct deposition on glass. Among the compositions studied, Ag$_{95}$Au$_5$ thin films exhibit the highest chemical stability, lowest optical losses in the visible spectral range, and excellent plasmonic properties even outcompeting pure Ag. As a proof-of-concept, we fabricate high-quality Ag$_{95}$Au$_5$ optical antennas that exhibit long-term durability under ambient conditions. Our approach provides a practical solution to overcome the limitations of Ag for plasmonic device applications.

cond-mat.mtrl-sci↗

arXiv2024

Frontier orbitals control dynamical disorder in molecular semiconductors

Charge transport in organic semiconductors is limited by dynamical disorder. Design rules for new high-mobility materials have therefore focused on limiting its two foundations: structural fluctuations and the transfer integral gradient. However, it has remained unclear how these goals should be translated into molecular structures. Here we show that a specific shape of the frontier orbital, with a lack of nodes along the long molecular axis, reduces the transfer integral gradient and therefore the dynamical disorder. We investigated single crystals of the prototypical molecular semiconductors pentacene and picene by angle-resolved photoemission spectroscopy and dynamical disorder calculations. We found that picene exhibits a remarkably low dynamical disorder. By separating in- and out-of-plane components of dynamical disorder, we identify the reason as a reduced out-of-plane disorder from a small transfer integral derivative. Our results demonstrate that molecules with an armchair $\pi$-electron topology and same-phase frontier orbitals like picene are promising molecular building blocks for the next generation of organic semiconductors.

cond-mat.mtrl-sci↗

arXiv2024

Excimer Formation in Zinc-phthalocyanine Revealed using Ultrafast Electron Diffraction

The formation of excited dimer states, so called excimers, is an important phenomenon in many organic molecular semiconductors. In contrast to Frenkel exciton-polaron excited states, an excimer is long-lived and energetically low-lying due to stabilization resulting from a substantial reorganization of the inter-molecular geometry. In this letter, we show that ultrafast electron diffraction can follow the dynamics of solid-state excimer formation in polycrystalline thin films of a molecular semiconductor, revealing both the key reaction modes and the eventual structure of the emitting state. We study the prototypical organic semiconductor zinc-phthalocyanine (ZnPc) in its crystallographic $\alpha$-phase as a model excimeric system. We show, that the excimer forms in a two-step process starting with a fast dimerization ($\lesssim 0.4\, \text{ps}$) followed by a subsequent slow shear-twist motion ($14\, \text{ps}$) leading to an alignment of the $\pi$-systems of the involved monomers. Furthermore, we show that while the same excimer geomtry is present in partially fluorinated derivatives of ZnPc, the formation kinematics slow down with increasing level of fluorination.

physics.chem-ph↗

arXiv2024

Surface doping of rubrene single crystals by molecular electron donors and acceptors

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

cond-mat.mtrl-sci↗

arXiv2022

Spectroscopic analysis of vibrational coupling in multi-molecular excited states

Multi-molecular excited states accompanied by an intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example excimers or charge transfer states. Understanding the dynamics of these states is crucial to improve organic devices such as light emitting diodes and solar cells. Their full microscopic description, however, demands for sophisticated tools such as ab-initio quantum chemical calculations which come at the expenses of high computational costs and are prone to errors by assumptions as well as iterative algorithmic procedures. Hence, the analysis of spectroscopic data is often conducted on a phenomenological level only. Here, we present a toolkit to analyze temperature dependent luminescence data and gain first insights into the relevant microscopic parameters of the molecular system at hand. By means of a Franck-Condon based approach considering a single effective inter-molecular vibrational mode and different potentials for the ground and excited state we are able to explain the luminescence spectra of such multi-molecular states. We demonstrate that by applying certain reasonable simplifications the luminescence of charge transfer states as well as excimers can be satisfactorily reproduced for temperatures ranging from cryogenics to above room temperature. We present a semi-classical and a quantum-mechanical description of our model and, for both cases, demonstrate its applicability by analyzing the temperature depended luminescence of the amorphous donor-acceptor heterojunction tetraphenyldibenzoperiflanthene:C$_{60}$ as well as polycrystalline zinc-phthalocyanine to reproduce the luminescence spectra and extract relevant system parameters such as the excimer binding energy.

cond-mat.mtrl-sci↗

arXiv2022

Orbital-resolved Observation of Singlet Fission

Singlet fission may boost photovoltaic efficiency [by transforming a singlet exciton into two triplet excitons and thereby doubling the number of excited charge carriers. The primary step of singlet fission is the ultrafast creation of the correlated triplet pair. While several mechanisms have been proposed to explain this step, none has emerged as a consensus. The challenge lies in tracking the transient excitonic states. Here we use time- and angle-resolved photoemission spectroscopy to observe the primary step of singlet fission in crystalline pentacene. Our results suggest a charge-transfer mediated mechanism with a hybridization of Frenkel and charge-transfer states in the lowest bright singlet exciton. We gained intimate knowledge about the localization and the orbital character of the exciton wave functions recorded in momentum maps. This allowed us to directly compare the localization of singlet and bitriplet excitons and decompose energetically overlapping states based on their orbital character. Orbital- and localization- resolved many-body dynamics promise deep insights into the mechanics governing molecular systems and topological materials.

cond-mat.mtrl-sci↗

arXiv2020

Nuclear dynamics of singlet exciton fission: a direct observation in pentacene single crystals

Singlet exciton fission (SEF) is a key process in the development of efficient opto-electronic devices. An aspect that is rarely probed directly, and yet has a tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynamics simulations, time-dependent density functional theory and experimental structure factor analysis, the coherent motions are identified as collective sliding motions of the pentacene molecules along their long axis. Such motions modify the excitonic coupling between adjacent molecules. Our findings reveal that long-range motions play a decisive part in the disintegration of the electronically correlated triplet pairs, and shed light on why SEF occurs on ultrafast timescales.

physics.chem-ph↗

arXiv2018

The new Felsenkeller 5 MV underground accelerator

The field of nuclear astrophysics is devoted to the study of the creation of the chemical elements. By nature, it is deeply intertwined with the physics of the Sun. The nuclear reactions of the proton-proton cycle of hydrogen burning, including the 3He({\alpha},{\gamma})7Be reaction, provide the necessary nuclear energy to prevent the gravitational collapse of the Sun and give rise to the by now well-studied pp, 7Be, and 8B solar neutrinos. The not yet measured flux of 13N, 15O, and 17F neutrinos from the carbon-nitrogen-oxygen cycle is affected in rate by the 14N(p,{\gamma})15O reaction and in emission profile by the 12C(p,{\gamma})13N reaction. The nucleosynthetic output of the subsequent phase in stellar evolution, helium burning, is controlled by the 12C({\alpha},{\gamma})16O reaction. In order to properly interpret the existing and upcoming solar neutrino data, precise nuclear physics information is needed. For nuclear reactions between light, stable nuclei, the best available technique are experiments with small ion accelerators in underground, low-background settings. The pioneering work in this regard has been done by the LUNA collaboration at Gran Sasso/Italy, using a 0.4 MV accelerator. The present contribution reports on a higher-energy, 5.0 MV, underground accelerator in the Felsenkeller underground site in Dresden/Germany. Results from {\gamma}-ray, neutron, and muon background measurements in the Felsenkeller underground site in Dresden, Germany, show that the background conditions are satisfactory for nuclear astrophysics purposes. The accelerator is in the commissioning phase and will provide intense, up to 50{\mu}A, beams of 1H+, 4He+ , and 12C+ ions, enabling research on astrophysically relevant nuclear reactions with unprecedented sensitivity.

physics.acc-ph↗

arXiv2017

Scalable Transfer-Free Fabrication of MoS$_2$/SiO$_2$ Hybrid Nanophotonic Cavity Arrays with Quality Factors Exceeding 4000

We report the fully-scalable fabrication of a large array of hybrid molybdenum disulfide (MoS$_2$) - silicon dioxide (SiO$_2$) one-dimensional, free-standing photonic-crystal cavities capable of enhancement of the MoS$_2$ photoluminescence at the narrow cavity resonance. We demonstrate continuous tunability of the cavity resonance wavelength across the entire emission band of MoS$_2$ simply by variation of the photonic crystal periodicity. Device fabrication started by substrate-scale growth of MoS$_2$ using chemical vapor deposition (CVD) on non-birefringent thermal oxide on a silicon wafer; it was followed by lithographic fabrication of a photon crystal nanocavity array on the same substrate at more than 50% yield of functional devices. Our cavities exhibit three dominant modes with measured linewidths less than 0.2 nm, corresponding to quality factors exceeding 4000. All experimental findings are found to be in excellent agreement with finite difference time domain simulations.

cond-mat.mes-hall↗