arXiv subjects

Roman Krahne

Publications and source records attributed to Roman Krahne.

At least 19 recordsLinked to original sources

arXiv2026

Nanoporous Copper Films as Platform for UV-SERS: Sensitivity and Ability to Perform Chiral Discrimination

Surface enhanced Raman spectroscopy (SERS) in the ultraviolet (UV) region offers important advantages for biomolecular detection, including resonance enhancement and reduced fluorescence interference. However, the development of UV SERS substrates that combine low cost, reproducibility, and chemical stability remains challenging. Here, we employ a dry synthesis approach to fabricate nanoporous Cu and copper oxide (CuO) films on silicon substrates and systematically evaluate their UV SERS performance using adenine as a Raman reporter under 325 nm excitation. Among the substrates investigated, nanoporous Cu exhibits the strongest enhancement, enabling adenine detection down to 10 microM. In contrast, no detectable adenine Raman signal is observed under 532 nm excitation, indicating that the enhancement is dominated by a UV induced chemical, charge transfer mechanism rather than conventional electromagnetic enhancement. The Cu substrates further enable the UV Raman spectroscopy of streptavidin, as a test protein, and, more interestingly, the discrimination between L and D tryptophane based solely on differences in UV SERS intensity, without chiral selectors or additional surface functionalization. By varying the substrate rotation speed during metal evaporation, the enantioselective response can be tuned, yielding L over D intensity ratios from 1.10 to 2.35 and demonstrating the critical role of substrate morphology in chiral discrimination. The dry synthesized nanoporous films provide a simpler, scalable, and ligand free fabrication strategy while offering additional capability for enantioselective detection. These findings establish dry processed nanoporous Cu films as promising platforms for UV-SERS biosensing and label free chiral analysis.

physics.app-ph↗

arXiv2026

Voltage-Controlled Phosphate Precipitation Gating in Solid-State Nanopore Memristors

Nanofluidic memristors preserve a record of electrical activity via ion migration and alterations in conductance that depend on the history of the device s state. These characteristics make them suitable for aqueous, energy efficient, and biologically compatible neuromorphic systems. To establish the viability of fluidic memristors for mimicking the brain s dynamic behavior, a more thorough understanding of the memristive materials and the underlying switching processes is required. In this study, we systematically examined a recently introduced memristive device based on inpore chemical reactions, where the combined influence of electrolyte composition and pore architecture on precipitation gated memory remains poorly understood. To address this, we constructed an asymmetric electrochemical system using CaCl2 and phosphate solutions separated by SiNx solid state nanopores. We explored how variations in pH, phosphate concentration, pore geometry, and voltage pulsing regimens affect the electrical characteristics and memristive performance. Comparison of the single pore and the array showed that parallel pores produced smoother pH and concentration dependent hysteresis and pulse responses, whereas the single pore retained larger, nonmonotonic changes.

physics.app-ph↗

arXiv2026

Ultrafast excitation of Bloch plasmon polaritons in hyperbolic metamaterials with an extreme ultra-violet transient grating

Manipulating materials properties with light drives advances in materials science and photonics. Hyperbolic metamaterials are promising candidates as next-generation quantum optical media. They support Bloch plasmon polaritons, which are characterized by potentially infinite wave-vectors and long lifetimes, but cannot be excited through direct light illumination due to momentum mismatch. Here, we experimentally show that a transient grating, formed via interference of fully coherent seeded free-electron laser pulses in a thin insulator film, enables the excitation of Bloch plasmon polaritons in an underlying hyperbolic metamaterial. Finite element simulations confirm the role of the transient grating in facilitating phase-matching and mode excitation. Our findings demonstrate a route to spatiotemporally excite Bloch plasmon polaritons modes, offering an alternative to permanently nanostructured gratings and potentially enabling ultrafast control of optical modes excitation.

physics.optics↗

arXiv2026

Deterministic nucleation of nanocrystal superlattices on 2D perovskites for light-funneling heterostructures

Semiconductor heterostructures that combine components with different dimensionality provide an interesting way to manipulate the physical properties of the resulting material. Two-dimensional lead halide perovskites crystallize as flat microcrystals and have efficient in-plane exciton mobility, while perovskite nanocrystals are efficient emitters with a tunable bandgap that can self-assemble into microscopic superlattices. However, combining such intricate architectures into heterostructures has been challenging due to the mismatch in solubility properties and the challenging transfer procedures. Here we realize heterostructures where CsPbBr3 nanocrystal superlattices are deterministically grown along the faces of PEA2PbBr4 two-dimensional layered perovskite microcrystals. The growth can be limited to the lateral faces of the microcrystals and result in core-crown epitaxial heterostructures, or extended to the vertical direction leading to core-shell-like structures. The growth method is simple yet effective and versatile, and promises to be expanded to a large variety of other materials. We demonstrate that these heterostructures can be employed as efficient light-harvesting systems. In fact, energy can be transferred from the two-dimensional microcrystal domain to the superlattices, enabling switching between linear and non-linear carrier recombination regimes by tuning the excitation fluence. Moreover, by exploiting the lifetime shortening of CsPbBr3 nanocrystal emission upon sample cooling, we ensure that energy transfer occurs after the biexcitonic and single-excitonic decays of the nanocrystals, effectively extending the radiative recombination of superlattices.

cond-mat.mtrl-sci↗

arXiv2026

Phase Transitions in Low-Dimensional Layered Double Perovskites: The Role of the Organic Moieties

Halide double perovskites are an interesting alternative to Pb-containing counterparts as active materials in optoelectronic devices. Low-dimensional double perovskites are fabricated by introducing large organic cations, resulting in organic/inorganic architectures with one or more inorganic octahedral layers separated by organic cations. Here, we synthesize layered double perovskites based on 3D Cs2AgBiBr6 that consist of double (2L) or single (1L) inorganic octahedral layers, using ammonium cations of different size and chemical structure. Temperature-dependent Raman spectroscopy reveals phase transition signatures in both inorganic lattice and organic moieties by detecting variations in their vibrational modes. Changes in the conformational arrangement of the organic cations to an ordered state coincide with a phase transition in the 1L systems with the shortest ammonium moieties. Significant changes of photoluminescence intensity observed around the transition temperature suggest that optical properties may be deeply affected by the octahedral tilts emerging at the phase transition.

cond-mat.mtrl-sci↗

arXiv2025

Heterostructure Design in Two-Dimensional Perovskites by Sequential Recrystallization

Low-dimensional metal halide perovskites provide exciting opportunities to fabricate new semiconductor materials. Semiconductor technology relies on electronic heterojunctions, and cost-efficient and flexible approaches to realize functional heterostructures are of fundamental importance. Lateral heterostructures define the energy landscape in the plane of the semiconducting lattice in such 2D materials, representing an ideal platform to tailor energy barriers and to control charge carrier flow. Here, we demonstrate a versatile one-pot synthesis to fabricate a large variety of 2D perovskite heterostructures based on different halides and/or metal cations. Exploiting sequential crystallization of different 2D perovskites, and playing with the composition and injection events of the materials, enables the design of diverse heterostructure architectures including multiple heterojunctions. We obtain crystalline quality of the heterojunctions, multicolor emission, and optical coupling between the different heterostructure regions. We foresee that the design freedom of our method will stimulate the development of novel optoelectronic devices where electronic band engineering is crucial.

cond-mat.mtrl-sci↗

arXiv2025

Plasmonic nanopore to monitor in-pore chemistry

In solid-state nanopores, achieving reliable control over pore aperture opening and closing (gating) remains a major challenge. Gating can be driven by the applied voltage involving electrically tunable chemical reactions, achieved by selecting appropriate compounds within the nanopore volume. In particular, cyclic precipitation and dissolution of metal phosphates can be triggered by regulating cation transport through an applied transmembrane voltage, thereby enabling reversible pore gating. Under negative bias, metal phosphate precipitates form inside the pore, obstructing ion flow and reducing current. Switching the polarity dissolves the precipitates, restoring ionic conductance. This process effectively produces a nanofluidic diode characterized by a remarkably high rectification ratio. To probe these localized chemical reactions more directly, we employed a plasmonic nanopore that generates strong confined fields, enabling surface-enhanced Raman scattering (SERS) measurements within the nanopore volume during cyclic gating. These measurements not only validate the proposed in-pore chemistry but also highlight the potential of plasmonic nanopores as powerful tools for monitoring nanoscale chemical processes with high spatial resolution.

physics.app-ph↗

arXiv2025

Probing Electro-Magnetic Field Enhancement in 3D Plasmonic Nanopores Using DNA-PAINT and Nanorulers

Plasmonic nanopores combine nanofluidic confinement with electromagnetic field enhancement, enabling optical interrogation of single molecules in sub-wavelength volumes. Yet, direct optical readout within these metallic geometries has remained challenging due to fluorescence quenching near the surface. Here, we implement DNA-PAINT as a molecular reporter of local optical fields inside plasmonic nanopores. Transient hybridization of fluorescent imager strands at the nanopore tips yields stochastic emission bursts that map active binding sites with nanometric precision. By varying the fluorophore-metal distance using DNA spacers of controlled length, we observe a non-monotonic intensity response consistent with near-field quenching and plasmonic enhancement, identifying an optimal separation of around 6 nm. Finally, we extend the concept to dual-material Au/Si nanopores, demonstrating lateral coupling between plasmonic and semiconducting regions. These results establish DNA-PAINT as a quantitative probe of nanoscale optical environments in hybrid nanopores.

physics.app-ph↗

arXiv2025

Layered Bimetal Nanoporous Platforms for SERS Sensing

Nanoporous metals are extensively investigated as platforms for applications in plasmonics. They present high surface areas and strong local electric fields that can be tuned at different energies, playing with the choice of the metals and the morphology of the porous layers. Until recently, research in the field of plasmonics has primarily focused on porous metals composed of a single element, with limited attention given to the impact of alloy composition. The investigation of bi-metallic systems has only just begun to emerge in the literature. In particular, combining two or more different plasmonic metals, it could be possible to explore the interactions between two metals excited at specific energies. This involves plasmonic coupling, electron transfer, band hybridization at the interface, electromagnetic field interactions, and possibly thermal and electronic energy transfer depending on separation, size, and materials involved. The analysis of bi-metal systems can also be interesting in biomolecule detection, such as in the case of Surface Enhanced Raman Scattering (SERS). Here we report, for the first time, a detailed study (comprising morphological analyses, numerical modelling, and optical spectroscopies) on bi-metal nanoporous platforms prepared with a dry-synthesis method enabling the easy and controllable fabrication of bilayers combining different metals such as Au, Ag, and Cu.

physics.app-ph↗

arXiv2025

Molecularly imprinted nanopores for multiplexed sensing, release, and in-edge computing

In nanopore technology, the development of multiplexed detection and release platforms with high spatial and temporal resolution remains a significant challenge due to the difficulty in distinguishing signals originating from different nanopores in a single chip. In this work, we present a solid-state nanopore system functionalized with molecularly imprinted polymers (MIPs) for the selective detection and controlled release of neurotransmitters. We designed a nanopore array where each nanopore is functionalized with a specific MIP able to recognize specific neurotransmitters (dopamine, gamma-aminobutyric acid, and histamine, respectively). The platform demonstrated high performance in terms of sensitivity, selectivity, recovery, and stability. Multiplexed detection with high spatiotemporal resolution of the order of 100 ms/ 3 {\mu}m was achieved by specifically depositing MIPs and conductive hydrogels on different nanopores prepared on a single solid-state membrane. The employment of micro-chambers for each nanopore prevented signal cross-talk, thereby enabling simultaneous detection and release of multiple neurotransmitters. Moreover, we demonstrated computing with different logic gates and in-edge computing. This nanopore platform represents a radically novel approach towards hybrid solid-state nanopores able to perform real-time label-free multiplex detection, controlled biomolecule release, and ionic logic computing, addressing key challenges in neurochemical sensing and bio-computation.

physics.app-ph↗

arXiv2025

Gated MoS2/SiN Nanochannel for Tunable Ion Transport and Protein Translocation

Ionic transport in nanofluidic channels holds great promise for applications such as single-molecule analysis, molecular manipulation, and energy harvesting. However, achieving precise control over ion transport remains a major challenge. In this work, we introduce a MoS2 SiN hybrid nanochannel architecture that enables electrical tuning of ionic transport via external gating, and we examine its potential for osmotic power generation and single molecule detection. To fabricate the channels, we employed a combined focused ion beam (FIB) milling and dry transfer method, producing sub 10 nm thick structures while preserving the structural integrity and electronic properties of MoS2, essential for reliable surface charge modulation. We first investigated how the gate voltage influences ionic conductance, finding evidence of gate dependent modulation of ion selectivity under different bias polarities. Next, by applying a salt concentration gradient across the nanochannels, we demonstrated the feasibility of this platform for osmotic energy harvesting. Finally, we tested the system for single molecule sensing, showing that linearized bovine serum albumin (BSA) produced translocation signals with notably long dwell times. Together, these results highlight gated MoS2 SiN nanochannels as a promising platform for tunable nanofluidics, with potential applications in controlled molecular transport and energy harvesting from osmotic gradients.

physics.app-ph↗

arXiv2025

Transformable Plasmonic Helix with Swinging Gold Nanoparticles

Control over multiple optical elements that can be dynamically rearranged to yield substantial three-dimensional structural transformations is of great importance to realize reconfigurable plasmonic nanoarchitectures with sensitive and distinct optical feedback. In this work, we demonstrate a transformable plasmonic helix system, in which multiple gold nanoparticles (AuNPs) can be directly transported by DNA swingarms to target positions without undergoing consecutive stepwise movements. The swingarms allow for programmable AuNP translocations in large leaps within plasmonic nanoarchitectures, giving rise to tailored circular dichroism spectra. Our work provides an instructive bottom-up solution to building complex dynamic plasmonic systems, which can exhibit prominent optical responses through cooperative rearrangements of the constituent optical elements with high fidelity and programmability.

physics.bio-ph↗

arXiv2025

Dynamics of DNA-Templated Ultrafine Silver Nanowires Formation

Recent research on silver nanowires prepared on DNA templates has focused on two fundamental applications: nano-scale circuits and sensors. Despite its broad potential, the formation kinetics of DNA-templated silver nanowires remains unclear. Here, we present an experimental demonstration of the formation of silver nanowires with a diameter of 2.2+0.4 nm at the single-molecule level through chemical reduction. We conducted equilibrium and perturbation kinetic experiments to measure force spectroscopy during the formation of Ag+ -DNA complexes and Ag-DNA complexes, using optical tweezers combined with microfluidics. The addition of AgNO3 resulted in an increase in force of 5.5-7.5 pN within 2 minutes, indicating that Ag+ compacts the DNA structure. In contrast, the addition of hydroquinone caused the force to decrease by 4-5 pN. Morphological characterization confirmed the presence of a dense structure formed by silver atoms bridging the DNA strands, and revealed conformational differences before and after metallization. We compare our experimental data with Brownian dynamics simulations using a coarse-grained double-stranded DNA (dsDNA) model that provides insights on the dependency of the force on the persistence length.

physics.app-ph↗

arXiv2024

Copper-based disordered plasmonic system with dense nanoisland morphology

Dry synthesis is a highly versatile method for the fabrication of nanoporous metal films, since it enables easy and reproducible deposition of single or multi-layer(s) of nanostructured materials that can find intriguing applications in plasmonics, photochemistry and photocatalysis, to name a few. Here, we extend the use of this methodology to the preparation of copper nanoislands that represent an affordable and versatile example of disordered plasmonic substrate. We perform detailed characterizations of the system using several techniques such as spectroscopic ellipsometry, cathodoluminescence, electron energy loss spectroscopy, ultrafast pump-probe spectroscopy and second-harmonic generation with the aim to investigate the optical properties of these systems in an unprecedented systematic way. Our study represents the starting point for future applications of this new disordered plasmonic system ranging from sensing to photochemistry and photocatalysis.

physics.app-ph↗

arXiv2024

Interplay of phonon directionality and emission polarization in two-dimensional layered metal halide perovskites

With polarized and angle-resolved Raman spectroscopy studies on single two-dimensional layered perovskites (2DLP) flakes with different ammonium molecules as organic cations, in 2020 we revealed the very rich phonon spectra in the low-frequency regime. Although the phonon bands at low frequency can generally be attributed to the vibrations of the inorganic lattice, we found very different phonon spectra for the same lead-bromide octahedra composition by only changing the type of the organic cations. In addition, the intensity of the different phonon modes depended strongly on the angle of the linearly polarized excitation beam with respect to the in-plane axes of the octahedra lattice. In 2022, we mapped this angular dependence of the phonon modes, which enabled to identify the directionality of the different lattice vibrations. By correlating the phonon spectra with the temperature-dependent emission for a set of 2DLPs that featured very different STE emission, we demonstrated that the exciton relaxation cannot be related to coupling with a single (longitudinal optical) phonon band, and that several phonon bands should be involved in the emission process. We performed angle-resolved polarized emission and Raman spectroscopy on the same two-dimensional lead iodide perovskite microcrystals, which revealed the impact of the organic cations on the linear polarization of the emission, and corroborated our interpretation that multiple phonon bands should be involved in the radiative recombination process. Our studies revealed a wealth of highly directional low-frequency phonons in 2DLPs from which several bands are involved in the emission process, which leads to diverse optical and vibrational properties depending on the type of organic cation in the material.

cond-mat.mtrl-sci↗

arXiv2024

Modular plasmonic nanopore for opto-thermal gating

Solid-state nanopore gating inspired by biological ion channels is gaining increasing traction due to a large range of applications in biosensing and drug delivery. Integration of stimuli-responsive molecules such as poly(N-isopropylacrylamide) (PNIPAM) inside nanopores can enable temperature-dependent gating, which so far has only been demonstrated using external heaters. In this work, we combine plasmonic resonators inside the nanopore architecture with PNIPAM to enable optical gating of individual or multiple nanopores with micrometer resolution and a switching speed of few milliseconds by thermo-plasmonics. We achieve a temperature change of 40 kelvin per millisecond and demonstrate the efficacy of this method using nanopore ionic conductivity measurements that enables selective activation of individual nanopores in an array. Moreover, the selective gating of specific nanopores in an array can set distinct ionic conductance levels: low, medium, and high (i.e., 0, 1, and 2), which could be exploited for logical gating with optical signal control. Such selective optical gating in nanopore arrays marks a breakthrough in nanofluidics, as it paves the way towards smart devices that offer multifunctional applications including biosensing, targeted drug delivery, and fluidic mixing.

physics.app-ph↗

arXiv2024

Tailored Fabrication of 3D Nanopores with Dielectric Oxides for Multiple Nanoscale Applications

Nanopore sensing is a key technology for single-molecule detection and analysis. Solid-state nanopores have emerged as a versatile platform, since their fabrication allows to engineer their properties by controlling size, shape, and chemical functionalization. However, lithography-based fabrication approaches for non-planar nanopores-on-chip rely on polymers that have limits with respect to hard- and robustness, durability, and refractive index. In this respect, nanopores made of metal oxides with high dielectric constant would be much more favourable and have the potential to extend the suitability of solid-state nanopores towards optoelectronic technologies. Here, we present a versatile method to fabricate three-dimensional nanopores of different dielectric oxides with controlled shapes. Our approach uses photoresist only as a template in the focused-ion-beam lithography to define the nanopore shape, which is subsequently coated with different oxides (SiO2, Al2O3, TiO2 and HfO2) by atomic-layer deposition. Then the photoresist is fully removed by chemo-physical treatment, resulting in nanopores entirely made from dielectric oxides on a thin solid-state membrane. Our methodology allows straightforward fabrication of convex, straight, and concave nanopore shapes that can be employed in various technologies and applications. We explored their performance as ionic nanochannels and investigated the dependence of the ionic current rectification on the nanopore geometry. We found hysteresis in the ionic conductance that enables potential applications of the nanopores in memristors. We also investigated the dielectric oxide nanopores for DNA sensing by measuring both cis-trans and trans-cis translocations and support our data with numerical simulations based on the Poisson-Nernst-Planck model.

physics.app-ph↗

arXiv2024

Phonon Directionality Impacts Electron-Phonon Coupling and Polarization of the Band-Edge Emission in Two-Dimensional Metal Halide Perovskites

Two-dimensional metal-halide perovskites are highly versatile for light-driven applications due to their exceptional variety in material composition, which can be exploited for tunability of mechanical and optoelectronic properties. The band edge emission is defined by structure and composition of both organic and inorganic layers, and electron-phonon coupling plays a crucial role in the recombination dynamics. However, the nature of the electron-phonon coupling and which kind of phonons are involved is still under debate. Here we investigate the emission, reflectance and phonon response from single two-dimensional lead-iodide microcrystals with angle-resolved polarized spectroscopy. We find an intricate dependence of the emission polarization with the vibrational directionality in the materials, which reveals that several bands of the low-frequency phonons with non-orthogonal directionality contribute to the band edge emission. Such complex electron-phonon coupling requires adequate models to predict the thermal broadening of the emission and provides opportunities to design its polarization properties.

cond-mat.mtrl-sci↗