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Boya Radha

Publications and source records attributed to Boya Radha.

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Observation of long-lived spin order in nanoconfined water

Liquids confined to nanometer-scale geometries exhibit behavior that departs markedly from their bulk counterparts, yet studying their dynamics under controlled conditions remains experimentally challenging. Here, we use nitrogen-vacancy (NV) center nuclear magnetic resonance (NMR) spectroscopy to probe water confined in 5.6 nm channels as a function of temperature. The system remains liquid throughout the investigated temperature range and exhibits strongly suppressed diffusivity, enabling direct detection of its 1H NMR spectrum. Occasionally, the proton resonance transforms into a doublet with a splitting of several tens of kilohertz, which we tentatively attribute to hyperfine interactions mediated by long-lived paramagnetic charge complexes, in turn seeded by solvated electrons optically injected during laser illumination. The intermittent appearance of this feature suggests a metastable state comprising a correlated population of charge-hydration complexes extending throughout the confined liquid.

cond-mat.mes-hall

Enhanced Ionic Conductivity of confined Ionic-Liquid in Angstrom-scale 2D channels

Understanding ion-transport under molecular confinement is essential for developing next-generation energy technologies, where ionic motion often occurs within nanoscale or angstrom-scale channels. In this study, we use the model system of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIM]+[TFSI]-) confined within angstrom-scale slit-shaped 2D channels fabricated via van der Waals assembly to exemplify a broader class of confined ionic liquids.This system provides a well-defined platform to unravel generic features of ion transport under extreme confinement. By systematically varying the channel height h, we demonstrate a non-monotonic conductivity dependence on confinement, with a maximum 26.7 S/m at confining height, 1.02 nm, over 30 times of the bulk value for these ionic liquids. The variation of conductivity with confinement arises from structural rearrangements of ionic layers in the slit channel. Enhanced values of conductivity occur under confinements that promote the breakup of ion pairs and larger clusters, thereby increasing the number of free ions. Stronger confinement (h, 0.68 nm) also leads to steric hindrance, lowering conductivity below bulk values. Furthermore, introducing co-solvents with a higher dielectric constant and lower viscosity, such as acetonitrile (ACN), amplifies conductivity to ~145 S/m. Comparative studies using ACN, dimethyl carbonate and diethyl carbonate highlight that both large dielectric constant and low viscosity critically govern ion transport under confinement, as also supported by molecular dynamics simulations. Overall, this work establishes confined [EMIM]+[TFSI]- as a representative system for probing mechanisms of nano- and angstrom-scale ion transport, demonstrating how nanoconfinement and the solvent environment can be systematically tuned to manipulate ionic conductivity at the molecular level.

physics.chem-ph

Two-dimensional clay channels for tunable nanofluidic memristor

Dynamic reconfiguration of charge carriers in confined ion-channels under electrical stimulation produces memory effects, where the internal resistance depends on history of the electric field. Vermiculite nanofluidic devices harness this effect to store and process information within a single component. We report switching between distinct memory loops by tuning ion transport pathways, governed by asymmetrical device architecture and intrinsic surface-charge. Polarity-dependent memory switching between crossing-1 and crossing-2 loops is achieved solely by altering electrode configurations, without modifying electrolyte, channel surface chemistry or device structure: providing mechanistic insights into ionic memristors through a straightforward, experimental strategy. The memristive characteristics are demonstrated in both in-plane and out-of-plane channel configurations with channel lengths spanning from centimeters to micrometers length scales using re-stacked vermiculite membranes and further investigated for miniaturization with devices of nanometer scale channel lengths, fabricated via ultramicrotomy method. Furthermore, we demonstrate neuromorphic functionalities, including synaptic potentiation-depression and programmable memory retention, highlighting potential for bio-inspired computing systems. Cost-effective and scalable fabrication solution processed vermiculite membrane memristors pave the way for practical integration of nanofluidic memristors for neuromorphic computing applications.

cond-mat.mtrl-sci

An Open-Source Framework for Measurement and Analysis of Nanoscale Ionic Transport

Nanofluidic systems exploit nanometre-scale confinement in channels and pores to regulate ionic transport, enabling functionalities such as osmotic energy harvesting and neuromorphic ionic memory. Studying such confined transport requires both precise electrical instrumentation and careful data analysis, yet, in practice, measurements are still often taken with vendor software, exported as files, and processed later in separate environments. In this work, we bring these steps together in a unified Python-based framework built around three interoperable graphical user interfaces (GUIs) for nanochannel, nanopore and memristor experiments. The framework is organised into two functional parts, measurement and analysis. On the measurement side, two GUIs drive Keithley Source Meters to run continuous voltage sweeps and user-defined memristive pulse sequences, while providing live plots, configuration management and controlled shutdown routines. On the analysis side, a dedicated nanochannel and nanopore GUI reads raw I-V datasets, applies unit-consistent processing, extracts conductance and ion mobility, evaluates selectivity and osmotic power, and is complemented by a web-based calculator that performs the same mobility analysis without a local Python installation. All three GUIs are implemented in Python/Tkinter with modular plotting and logging layers so that flexible control sequences and physics-based post-processing share a common data format, improving reproducibility, timing stability and day-to-day efficiency in nanofluidic and electronic device studies.

cond-mat.mes-hall

Direct imaging elucidates ionic memory in two-dimensional nanochannels

Nanofluidic memristors promise brain-inspired information processing with ions, yet their microscopic origin remains debated. So far, ionic memory has been attributed to ion-specific interactions, dynamic wetting, chemical reactions or mechanical deformations, yet typically without direct experimental evidence. Here, by combining operando interferometric imaging with electrokinetic measurements, we directly visualize voltage-induced blistering of the confining walls of two-dimensional (2D) nanochannels, as key origin of memristive hysteresis. We identify two distinct classes of blisters: unidirectional, driven by electrostatic forces on surface charges, and bidirectional, arising from osmotic pressure due to concentration polarization. This mechanistic framework explains device evolution and device-to-device variability, and reframes stochastic blistering as a functional design element. Our results constitute a direct proof of electromechanical coupling as a robust pathway to ionic memory in 2D nanochannels and open routes toward high-performance ionic memristors and electrically actuated nanofluidic valves.

cond-mat.mes-hall

Slow water in engineered nano-channels revealed by color-center-enabled sensing

Nanoscale confinement of molecules in a fluid can result in enhanced viscosity, local fluidic order, or collective motion. Confinement also affects ion transport and/or the rate and equilibrium concentration in a chemical reaction, all of which makes it the subject of broad interest. Studying these effects, however, is notoriously difficult, mainly due to the lack of experimental methods with the required sensitivity and spatial or time resolution. Here we leverage shallow nitrogen-vacancy (NV) centers in diamond to probe the dynamics of room-temperature water molecules entrapped within ~6-nm-tall channels formed between the diamond crystal and a suspended hexagonal boron nitride (hBN) flake. NV-enabled nuclear magnetic resonance measurements of confined water protons reveal a much reduced H2O self-diffusivity, orders of magnitude lower than in bulk water. We posit the slow dynamics stem from the accumulation of photogenerated carriers at the interface and trapped fluid, a notion we support with the help of molecular dynamics modeling. Our results provide feedback for theories describing interfacial water, and lay out a route for investigating other fluids under confinement.

cond-mat.mes-hall

Fabrication of angstrom-scale two-dimensional channels for mass transport

Fluidic channels at atomic scales regulate cellular trafficking and molecular filtration across membranes and thus play crucial roles in the functioning of living systems. However, constructing synthetic channels experimentally at these scales has been a significant challenge due to the limitations in nanofabrication techniques and the surface roughness of the commonly used materials. Angstrom-scale slit-like channels address this challenge, as these can be made with precise control over their dimensions and can be used to study the fluidic properties of gases, ions and water at unprecedented scales. Here, we provide a detailed fabrication method of the two-dimensional (2D) angstrom-scale channels, which can be assembled as a single channel or up to hundreds of channels made with atomic scale precision using layered crystals. The procedure includes the fabrication of the substrate, flake, spacer layer, flake transfers, van der Waals assembly, and post-processing. We further explain how to perform molecular transport measurements with the angstrom-scale channels, for the development of methods directed at unravelling interesting and anomalous phenomena that help shed light on the physics of nanofluidic transport systems. The procedure requires a total of 1 to 2 weeks for the fabrication of the 2D channel device and is suitable for users with prior experience in clean room working environments and nanofabrication.

physics.app-ph

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

Stray magnetic field imaging of thin exfoliated iron halides flakes

Magnetic van der Waals materials are often proposed for use in future spintronic devices, aiming to leverage the combination of long-range magnetic order and near-atomic thinness to produce energy-efficient components. One class of material that has been discussed in this context are the iron halides FeCl$_2$ and FeBr$_2$, which are A-type antiferromagnets with strong uniaxial magnetocrystalline anisotropy. However, despite characterization of the bulk materials, the possibility for sustaining the magnetic behaviors that would underpin such applications in thin flakes has not been investigated. In this work, we use nitrogen-vacancy (NV) center microscopy to quantitatively image magnetism in individual exfoliated flakes of these iron halides, revealing the absence of magnetic remanence, a weak induced magnetization under bias field and variable behavior versus temperature. We show that our results are consistent with the antiferromagnetic behavior of the bulk material with a soft ferromagnetic uncompensated layer, indicating that extended ($>1~μ$m) ferromagnetic domains are not sustained even at low temperatures (down to 4 K). Finally, we find that the magnetic order is strongly affected by the sample preparation, with a surprising diamagnetic order observed in a thin, hydrated sample.

cond-mat.mtrl-sci

Beyond steric selectivity of ions using angstrom-scale capillaries

Ion-selective channels play a key role in physiological processes and are used in many technologies. While biological channels can efficiently separate same-charge ions with similar hydration shells, it remains a challenge to mimic such exquisite selectivity using artificial solid-state channels. Although, there are several nanoporous membranes that show high selectivity with respect to certain ions, the underlying mechanisms are based on the hydrated ion size and/or charge. There is a need to rationalize the design of artificial channels to make them capable of selecting between similar-size same-charge ions, which in turn requires understanding of why and how such selectivity can occur. To address this issue, we study angstrom-scale artificial channels made by van der Waals assembly, which are comparable in size with typical ions and carry little residual charge on channel walls. This allows us to exclude the first-order effects of steric and Coulomb-based exclusion. We show that the studied two-dimensional angstrom-scale capillaries can distinguish between same-charge ions with similar hydrated diameters. The selectivity is attributed to different positions occupied by ions within the layered structure of nanoconfined water, which depend on the ion-core size and differ for anions and cations. The revealed mechanism points at possibilities of ion separation beyond the simple steric sieving.

cond-mat.mes-hall

Strong electronic winds blowing under liquid flows on carbon surfaces

The interface between a liquid and a solid is the location of plethora of intrincate mechanisms at the nanoscale, at the root of their specific emerging properties in natural processes or technological applications. However, while the structural properties and chemistry of interfaces have been intensively explored, the effect of the solid-state electronic transport at the fluid interface has been broadly overlooked up to now. It has been reported that water flowing against carbon-based nanomaterials, such as carbon nanotubes or graphene sheets, does induce electronic currents, but the mechanism at stake remains controversial. Here, we unveil the molecular mechanisms underlying the hydro-electronic couplings by investigating the electronic conversion under flow at the nanoscale. We use a tuning fork-Atomic Force Microscope (AFM) to deposit and displace a micrometric droplet of both ionic and non-ionic liquids on a multilayer graphene sample, while recording the electrical current across the carbon flake. We report measurements of an oscillation-induced current which is several orders of magnitude larger than previously reported for water on carbon , and further boosted by the presence of surface wrinkles on the carbon layer. Our results point to a peculiar momentum transfer mechanism between fluid molecules and charge carriers in the carbon walls mediated by phonon excitations in the solid. Our findings pave the way for active control of fluid transfer at the nanoscale by harnessing the complex interplay between collective excitations in the solid and the molecules in the fluid.

cond-mat.mes-hall

Angstrofluidics: walking to the limit

Angstrom-scale fluidic channels are ubiquitous in nature, and play an important role in regulating cellular traffic, signaling, and responding to stimuli. Synthetic channels are now a reality with the emergence of several cutting-edge bottom-up and top-down fabrication methods. In particular, the use of atomically thin two dimensional (2D) materials and nanotubes as components to build fluidic conduits has pushed the limits of fabrication to the Angstrom-scale. Here, we provide an overview of the recent developments in the fabrication methods for nano- and angstrofluidic channels while categorizing them on the basis of dimensionality (0D pores, 1D tubes, 2D slits), along with the latest advances in measurement techniques. We discuss the ionic transport governed by various stimuli in these channels and draw comparison of ionic mobility, streaming and osmotic power, with varying pore sizes across all the dimensionalities. Towards the end of the review, we highlight the unique future opportunities in the development of smart ionic devices.

cond-mat.mes-hall

Hydrocarbon Contamination in Angstrom-scale Channels

Nonspecific molecular adsorption like airborne contamination occurs on most surfaces including those of 2D materials and alters their properties. While the surface contamination is studied using a plethora of techniques, the effect of contamination on a confined system such as nanochannels, nanopores leading to their clogging is still lacking. We report a systematic investigation of hydrocarbon adsorption in the angstrom slit channels of varied heights. Hexane is chosen to mimic the hydrocarbon contamination and the clogging of the angstrom-channels is evaluated via a Helium gas flow measurement. The level of the hexane adsorption, in other words, the degree of clogging depends on the size difference between the channels and hexane. A dynamic transition of the clogging and revival process is shown in sub-2 nm thin channels. Long-term storage and stability of our angstrom-channels is demonstrated here up to three years, alleviating the contamination and unclogging the channels using thermal treatment. This study highlights the importance of the nanochannels stability and demonstrates self-cleansing nature of sub-2 nm thin channels enabling a robust platform for molecular transport and separation studies. We provide a method to assess the cleanliness of the nanoporous membranes, which is vital for the practical applications of nanofluidics in various fields such as molecular sensing, separation and power generation.

physics.chem-ph

Molecular streaming and its voltage control in ångström scale channels

The field of nanofluidics has shown considerable progress over the past decade thanks to key instrumental advances, leading to the discovery of a number of exotic transport phenomena for fluids and ions under extreme confinement. Recently, van der Waals assembly of 2D materials allowed fabrication of artificial channels with angström-scale precision. This ultimate confinement to the true molecular scale revealed unforeseen behaviour for both mass and ionic transport. In this work, we explore pressure-driven streaming in such molecular-size slits and report a new electro-hydrodynamic effect under coupled pressure and electric force. It takes the form of a transistor-like response of the pressure induced ionic streaming: an applied bias of a fraction of a volt results in an enhancement of the streaming mobility by up to 20 times. The gating effect is observed with both graphite and boron nitride channels but exhibits marked material-dependent features. Our observations are rationalized by a theoretical framework for the flow dynamics, including the frictional interaction of water, ions and the confining surfaces as a key ingredient. The material dependence of the voltage modulation can be traced back to a contrasting molecular friction on graphene and boron nitride. The highly nonlinear transport under molecular-scale confinement offers new routes to actively control molecular and ion transport and design elementary building blocks for artificial ionic machinery, such as ion pumps. Furthermore, it provides a versatile platform to explore electro-mechanical couplings potentially at play in recently discovered mechanosensitive ionic channels.

cond-mat.soft