arXiv subjects

Martina Lihter

Publications and source records attributed to Martina Lihter.

7 recordsLinked to original sources

arXiv2024

Monitoring electrochemical dynamics through single-molecule imaging of hBN surface emitters in organic solvents

Electrochemical techniques conventionally lack spatial resolution and average local information over an entire electrode. While advancements in spatial resolution have been made through scanning probe methods, monitoring dynamics over large areas is still challenging, and it would be beneficial to be able to decouple the probe from the electrode itself. In this work, we leverage single molecule microscopy to spatiotemporally monitor analyte surface concentrations over a wide area using unmodified hexagonal boron nitride (hBN) in organic solvents. Through a sensing scheme based on redox-active species interactions with fluorescent emitters at the surface of hBN, we observe a linear decrease in the number of emitters under positive voltages applied to a nearby electrode. We find consistent trends in electrode reaction kinetics vs overpotentials between potentiostat-reported currents and optically-read emitter dynamics, showing Tafel slopes greater than 290 mV per decade. Finally, we draw on the capabilities of spectral single molecule localization microscopy (SMLM) to monitor the fluorescent species identity, enabling multiplexed readout. Overall, we show dynamic measurements of analyte concentration gradients at a micrometer-length scale with nanometer-scale depth and precision. Considering the many scalable options for engineering fluorescent emitters with 2D materials, our method holds promise for optically detecting a range of interacting species with unprecedented localization precision.

cond-mat.mes-hall↗

arXiv2023

Liquid-activated quantum emission from pristine hexagonal boron nitride for nanofluidic sensing

Liquids confined down to the atomic scale can show radically new properties. However, only indirect and ensemble measurements operate in such extreme confinement, calling for novel optical approaches enabling direct imaging at the molecular level. Here, we harness fluorescence originating from single-photon emitters at the surface of hexagonal boron nitride (hBN) for molecular imaging and sensing in nanometrically confined liquids. The emission originates from the chemisorption of organic solvent molecules onto native surface defects, revealing single-molecule dynamics at the interface through spatially correlated activation of neighboring defects. Emitter spectra further offer a direct readout of local dielectric properties, unveiling increasing dielectric order under nanometer-scale confinement. Liquid-activated native hBN defects bridge the gap between solid-state nanophotonics and nanofluidics, opening new avenues for nanoscale sensing and optofluidics.

cond-mat.mes-hall↗

arXiv2022

High-throughput nanopore fabrication and classification using FIB irradiation and automated pore edge analysis

Large-area nanopore drilling is a major bottleneck in state-of-the-art nanoporous 2D membrane fabrication protocols. In addition, high-quality structural and statistical descriptions of as-fabricated porous membranes are key to predicting the corresponding membrane-wide permeation properties. In this work, we investigate Xe-ion focused ion beam as a tool for scalable, large-area nanopore fabrication on atomically thin, free-standing molybdenum disulphide. The presented irradiation protocol enables designing ultrathin membranes with tunable porosity and pore dimension, along with spatial uniformity across large-area substrates. Fabricated nanoporous membranes were characterized using scanning transmission electron microscopy imaging and the observed nanopore geometries were analyzed through a pore-edge detection script. We further demonstrated that the obtained structural and statistical data can be readily passed on to computational and analytical tools to predict the permeation properties at both individual pore and membrane-wide scales. As an example, membranes featuring angstrom-scale pores were investigated in terms of their emerging water and ion flow properties through extensive all-atom molecular dynamics simulations. We believe that the combination of experimental and analytical approaches presented here should yield accurate physics-based property estimates and thus potentially enable a true function-by-design approach to fabrication for applications such as osmotic power generation, desalination/filtration, as well as their strain-tunable versions.

cond-mat.mtrl-sci↗

arXiv2021

Direct growth of hexagonal boron nitride on photonic chips for high-throughput characterization

Adapting optical microscopy methods for nanoscale characterization of defects in two-dimensional (2D) materials is a vital step for photonic on-chip devices. To increase the analysis throughput, waveguide-based on-chip imaging platforms have been recently developed. Their inherent disadvantage, however, is the necessity to transfer the 2D material from the growth substrate to the imaging chip which introduces contamination, potentially altering the characterization results. Here we present a unique approach to circumvent these shortfalls by directly growing a widely-used 2D material (hexagonal boron nitride, hBN) on silicon nitride chips, and optically characterizing the defects in the intact as-grown material. We compare the direct growth approach to the standard wet transfer method, and confirm the clear advantages of the direct growth. While demonstrated with hBN in the current work, the method is easily extendable to other 2D materials.

physics.optics↗

arXiv2020

Electrochemical Surface Modification of a 2D MoS2 Semiconductor

The surface modification of 2D semiconducting materials, such as transition metal dichalcogenides (TMDCs), is becoming important for a diverse range of applications, such as biosensing, catalysis, energy generation and energy storage. Due to the chemical inertness of their basal plane, the surface modification of 2D TMDCs is mainly limited to their defective sites, or it requires a conversion of TMDC from its semiconducting into a metallic phase. In this work, we show that the basal plane of a 2D semiconductor molybdenum disulfide (MoS2) can be modified by electrochemical grafting of aryl-diazonium salt, such as 3,5-bis(trifluoromethyl)benzenediazonium tetrafluoroborate. To investigate the applicability of this method, we perform electrografting on MoS2 nanoribbons by addressing them individually via a different electrode. High spatial selectivity of this method on the nanoscale opens the possibility for specific surface modification of neighboring 2D layers and nanostructures that are contacted by electrodes. This method could be potentially applicable to other 2D semiconducting materials that are active in the same potential window in which the electrochemical reduction of aryl diazonium salts occurs.

physics.app-ph↗

arXiv2020

Super-resolved optical mapping of reactive sulfur-vacancy in 2D transition metal dichalcogenides

Transition metal dichalcogenides (TMDs) represent an entire new class of semiconducting 2D materials with exciting properties. Defects in 2D TMDs can crucially affect their physical and chemical properties. However, characterization of the presence and spatial distribution of defects is limited either in throughput or in resolution. Here, we demonstrate large area mapping of reactive sulfur-deficient defects in 2D-TMDs coupling single-molecule localization microscopy with fluorescence labeling using thiol chemistry. Our method, reminiscent of PAINT strategies, relies on the specific binding by reversible physisorption of fluorescent probes to sulfur-vacancies via a thiol group and their intermittent emission to apply localization of the labeled defects with a precision down to 15 nm. Tuning the distance between the fluorophore and the docking thiol site allows us to control Föster Resonance Energy Transfer (FRET) process and reveal large structural defects such as grain boundaries and line defects, due to the local irregular lattice structure. Our methodology provides a simple and fast alternative for large-scale mapping of non-radiative defects in 2D materials and paves the way for in-situ and spatially resolved monitoring of the interaction between chemical agent and the defects in 2D materials that has general implications for defect engineering in aqueous condition.

physics.app-ph↗

arXiv2019

Light Enhanced Blue Energy Generation using MoS$_2$ Nanopores

Blue energy relies on the chemical potential difference generated between solutions of high and low ionic strength and would provide a sun-and-wind independent energy source at estuaries around the world. Converting this osmotic energy through reverse-electrodialysis relies on ion-selective membranes. A novel generation of these membranes is based on atomically thin MoS$_2$ membranes to decrease the resistance to current flow to increase power output. By modulating the surface charge by light we are able to raise the ion selectivity of the membrane by a factor of 5 while staying at a neutral pH. Furthermore, we find that the behavior of small nanopores is dominated by surface conductance. We introduce a formalism based on the Dukhin number to quantify these effects in the case of a concentration gradient system. As a consequence, the charges created by light illumination provoke two important changes. Increased surface charge at the pore rim enhances the ion selectivity and therefore larger osmotic voltage (dominating in small pores), while the increased surface charge of the overall membrane enhances the surface conductance and therefore the osmotic current (dominating in larger pores). The combination of these effects might be able to efficiently boost the energy generation with arrays of nanopores with varying pore sizes.

physics.app-ph↗