arXiv subjects

Jan A. Mol

Publications and source records attributed to Jan A. Mol.

At least 19 recordsLinked to original sources

arXiv2024

Electron Phase Detection in Single Molecules by Interferometry

Interferometry has underpinned a century of discoveries, ranging from the disproval of the ether theory to the detection of gravitational waves, offering insights into wave dynamics with unrivalled precision through the measurement of phase relationships. In electronics, phase-sensitive measurements can probe the nature of transmissive topological and quantum states, but are only possible using complex device structures in magnetic fields. Here we demonstrate electronic interferometry in a single-molecule device through the study of non-equilibrium Fano resonances. We show the phase difference between an electronic orbital and a coupled Fabry-Perot resonance are tuneable through electric fields, and consequently it is possible to read out quantum information in the smallest devices, offering new avenues for the coherent manipulation down to single molecules.

physics.chem-ph↗

arXiv2023

Quantum Interference Enhances the Performance of Single-Molecule Transistors

An unresolved challenge facing electronics at a few-nm scale is that resistive channels start leaking due to quantum tunneling. This affects the performance of nanoscale transistors, with single-molecule devices displaying particularly low switching ratios and operating frequencies, combined with large subthreshold swings.1 The usual strategy to mitigate quantum effects has been to increase device complexity, but theory shows that if quantum effects are exploited correctly, they can simultaneously lower energy consumption and boost device performance.2-6 Here, we demonstrate experimentally how the performance of molecular transistors can be improved when the resistive channel contains two destructively-interfering waves. We use a zinc-porphyrin coupled to graphene electrodes in a three-terminal transistor device to demonstrate a >104 conductance-switching ratio, a subthreshold swing at the thermionic limit, a > 7 kHz operating frequency, and stability over >105 cycles. This performance is competitive with the best nanoelectronic transistors. We fully map the antiresonance interference features in conductance, reproduce the behaviour by density functional theory calculations, and trace back this high performance to the coupling between molecular orbitals and graphene edge states. These results demonstrate how the quantum nature of electron transmission at the nanoscale can enhance, rather than degrade, device performance, and highlight directions for future development of miniaturised electronics.

physics.chem-ph↗

arXiv2022

Electronic measurements of entropy in meso- and nanoscale systems

Entropy is one of the most fundamental quantities in physics. For systems with few degrees of freedom, the value of entropy provides a powerful insight into its microscopic dynamics, such as the number, degeneracy and relative energies of electronic states, the value of spin, degree of localisation and entanglement, and the emergence of exotic states such as non-Abelian anyons. As the size of a system decreases, the conventional methods for measuring entropy, based on heat capacity, quickly become infeasible due to the requirement of increasingly accurate measurements of heat. Several methods to directly measure entropy of mesoscopic quantum systems have recently been developed. These methods use electronic measurements of charge, conductance and thermocurrent, rather than heat, and have been successfully applied to a wide range of systems, from quantum dots and molecules, to quantum Hall states and twisted bilayer graphene. In this Review, we provide an overview of electronic direct entropy measurement methods, discuss their theoretical background, compare their ranges of applicability and look into the directions for their future extensions and applications.

cond-mat.mes-hall↗

arXiv2022

Phase-Coherent Charge Transport through a Porphyrin Nanoribbon

Quantum interference in nano-electronic devices could lead to reduced-energy computing and efficient thermoelectric energy harvesting. When devices are shrunk down to the molecular level it is still unclear to what extent electron transmission is phase coherent, as molecules usually act as scattering centres, without the possibility of showing particle-wave duality. Here we show electron transmission remains phase coherent in molecular porphyrin nanoribbons, synthesized with perfectly defined geometry, connected to graphene electrodes. The device acts as a graphene Fabry-Pérot interferometer, allowing direct probing of the transport mechanisms throughout several regimes, including the Kondo one. Electrostatic gating allows measurement of the molecular conductance in multiple molecular oxidation states, demonstrating a thousand-fold increase of the current by interference, and unravelling molecular and graphene transport pathways. These results demonstrate a platform for the use of interferometric effects in single-molecule junctions, opening up new avenues for studying quantum coherence in molecular electronic and spintronic devices.

cond-mat.mes-hall↗

arXiv2022

Mapping Conductance and Switching Behavior of Graphene Devices In Situ

Graphene has been proposed for use in various nanodevice designs, many of which harness emergent quantum properties for device functionality. However, visualization, measurement, and manipulation become non-trivial at nanometer and atomic scales, representing a significant challenge for device fabrication, characterization, and optimization at length scales where quantum effects emerge. Here, we present proof of principle results at the crossroads between 2D nanoelectronic devices, e-beam-induced modulation, and imaging with secondary electron e-beam induced currents (SEEBIC). We introduce a device platform compatible with scanning transmission electron microscopy investigations. We then show how the SEEBIC imaging technique can be used to visualize conductance and connectivity in single layer graphene nanodevices, even while supported on a thicker substrate (conditions under which conventional imaging fails). Finally, we show that the SEEBIC imaging technique can detect subtle differences in charge transport through time in non-ohmic graphene nanoconstrictions indicating the potential to reveal dynamic electronic processes.

cond-mat.mes-hall↗

arXiv2022

Charge-state dependent vibrational relaxation in a single-molecule junction

The interplay between nuclear and electronic degrees of freedom strongly influences molecular charge transport. Herein, we report on transport through a porphyrin dimer molecule, weakly coupled to graphene electrodes, that displays sequential tunneling within the Coulomb-blockade regime. The sequential transport is initiated by current-induced phonon absorption and proceeds by rapid sequential transport via a non-equilibrium vibrational distribution. We demonstrate this is possible only when the vibrational dissipation is slow relative to sequential tunneling rates, and obtain a lower bound for the vibrational relaxation time of 8 ns, a value that is dependent on the molecular charge state.

cond-mat.mes-hall↗

arXiv2021

Localised Solid-State Nanopore Fabrication via Controlled Breakdown using On-Chip Electrodes

Controlled breakdown has recently emerged as a highly accessible technique to fabricate solid-state nanopores. However, in its most common form, controlled breakdown creates a single nanopore at an arbitrary location in the membrane. Here, we introduce a new strategy whereby breakdown is performed by applying the electric field between an on-chip electrode and an electrolyte solution in contact with the opposite side of the membrane. We demonstrate two advantages of this method. First, we can independently fabricate multiple nanopores at given positions in the membrane by localising the applied field to the electrode. Second, we show we can create nanopores that are self-aligned with complementary nanoelectrodes by applying voltages to the on-chip electrodes to locally heat the membrane during controlled breakdown. This new controlled breakdown method provides a path towards the affordable, rapid, and automatable fabrication of arrays of nanopores self-aligned with complementary on-chip nanostructures.

physics.chem-ph↗

arXiv2021

Controlling the entropy of a single-molecule junction

Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics, that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements which can be used to determine the difference in configurational entropy between the redox states of a nanoscale system involved in conductance without any prior assumptions about its structure or microscopic dynamics.

cond-mat.mes-hall↗

arXiv2021

Single-electron transport in a molecular Hubbard dimer

Many-body electron interactions are at the heart of chemistry and solid-state physics. Understanding these interactions is crucial for the development of molecular-scale quantum and nanoelectronic devices. Here, we investigate single-electron tunneling through an edge-fused porphyrin oligomer and demonstrate that its transport behavior is well described by the Hubbard dimer model. This allows us to study the role of electron-electron interactions in the transport setting. In particular, we empirically determine the molecule's on-site and inter-site electron-electron repulsion energies, which are in good agreement with density functional calculations, and establish the molecular electronic structure within various charge states. The gate-dependent rectification behavior is used to further confirm the selection rules and state degeneracies resulting from the Hubbard model. We therefore demonstrate that current flow through the molecule is governed by a non-trivial set of vibrationally coupled electronic transitions between various many-body states, and experimentally confirm the importance of electron-electron interactions in single-molecule devices.

cond-mat.mes-hall↗

arXiv2021

Understanding Electrical Conduction and Nanopore Formation During Controlled Breakdown

Controlled breakdown has recently emerged as a highly appealing technique to fabricate solid-state nanopores for a wide range of biosensing applications. This technique relies on applying an electric field of approximately 0.6-1 V/nm across the membrane to induce a current, and eventually, breakdown of the dielectric. However, a detailed description of how electrical conduction through the dielectric occurs during controlled breakdown has not yet been reported. Here, we study electrical conduction and nanopore formation in SiN$_x$ membranes during controlled breakdown. We show that depending on the membrane stoichiometry, electrical conduction is limited by either oxidation reactions that must occur at the membrane-electrolyte interface (Si-rich SiN$_x$), or electron transport across the dielectric (stoichiometric Si$_3$N$_4$). We provide several important implications resulting from understanding this process which will aid in further developing controlled breakdown in the coming years, particularly for extending this technique to integrate nanopores with on-chip nanostructures.

physics.chem-ph↗

arXiv2019

Understanding resonant charge transport through weakly coupled single-molecule junctions

Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and it is now well understood within the framework of the non-interacting Landauer approach. Conversely, gaining a qualitative and quantitative understanding of the resonant transport regime has proven more elusive. Here, we study resonant charge transport through graphene-based zinc-porphyrin junctions. We experimentally demonstrate an inadequacy of the non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we model the overall charge transport as a sequence of non-adiabatic electron transfers, the rates of which depend on both outer and inner-sphere vibrational interactions. We show that the transport properties of our molecular junctions are determined by a combination of electron-electron and electron-vibrational coupling, and are sensitive to the interactions with the wider local environment. Furthermore, we assess the importance of nuclear tunnelling and examine the suitability of semi-classical Marcus theory as a description of charge transport in molecular devices.

cond-mat.mes-hall↗

arXiv2019

The role of metallic leads and electronic degeneracies in thermoelectric power generation in quantum dots

The power factor of a thermoelectric device is a measure of the heat-to-energy conversion efficiency in nanoscopic devices. Yet, even as interest in low-dimensional thermoelectric materials has increased, experimental research on what influences the power factor in these systems is scarce. Here, we present a detailed thermoelectric study of graphene quantum dot devices. We show that spin-degeneracy of the quantum dot states has a significant impact on the zero-bias conductance of the device and leads to an increase of the power factor. Conversely, we demonstrate that non-ideal heat exchange within the leads can suppress the power factor near the charge degeneracy point and non-trivially influences its temperature dependence.

cond-mat.mes-hall↗

arXiv2018

Geometrically Enhanced Thermoelectric Effects in Graphene Nanoconstrictions

The influence of nanostructuring and quantum confinement on the thermoelectric properties of materials has been extensively studied. While this has made possible multiple breakthroughs in the achievable figure of merit, classical confinement, and its effect on the local Seebeck coefficient has mostly been neglected, as has the Peltier effect in general due to the complexity of measuring small temperature gradients locally. Here we report that reducing the width of a graphene channel to 100 nm changes the Seebeck coefficient by orders of magnitude. Using a scanning thermal microscope allows us to probe the local temperature of electrically contacted graphene two-terminal devices or to locally heat the sample. We show that constrictions in mono- and bilayer graphene facilitate a spatially correlated gradient in the Seebeck and Peltier coefficient, as evidenced by the pronounced thermovoltage $V_{th}$ and heating/cooling response $ΔT_{Peltier}$, respectively. This geometry dependent effect, which has not been reported previously in 2D materials, has important implications for measurements of patterned nanostructures in graphene and points to novel solutions for effective thermal management in electronic graphene devices or concepts for single material thermocouples.

cond-mat.mes-hall↗

arXiv2018

Beyond Marcus theory and the Landauer-Büttiker approach in molecular junctions: A unified framework

Charge transport through molecular junctions is often described either as a purely coherent or a purely classical phenomenon, and described using the Landauer-Büttiker formalism or Marcus theory, respectively. Using a generalised quantum master equation, we here derive an expression for current through a molecular junction modelled as a single electronic level coupled to a collection of thermalised vibrational modes. We demonstrate that the aforementioned theoretical approaches can be viewed as two limiting cases of this more general expression, and present a series of approximations of this result valid at higher temperatures. We find that Marcus theory is often insufficient in describing the molecular charge transport characteristics and gives rise to a number of artefacts, especially at lower temperatures. Alternative expressions, retaining its mathematical simplicity but rectifying those shortcomings, are suggested. In particular, we show how lifetime broadening can be consistently incorporated into Marcus theory, and we derive a low-temperature correction to the semi-classical Marcus hopping rates. Our results are applied to examples building on phenomenological as well as microscopically-motivated electron-vibrational coupling. We expect them to be particularly useful in experimental studies of charge transport through single-molecule junctions as well as self-assembled monolayers.

cond-mat.mes-hall↗

arXiv2018

Quantum Interference in Silicon 1D Quasi-Ballistic Junctionless Nanowire Field Effect Transistors

We investigate the low temperature transport in 8 nm diameter Si junctionless nanowire field effect transistors fabricated by top down techniques with a wrap-around gate and two different activated doping densities. First we extract the intrinsic gate capacitance of the device geometry from a device that shows Coulomb blockade at 13 mK with over 500 Coulomb peaks across a gate voltage range of 6 V indicating the formation of a single island in the entire nanowire channel. In two other devices, doped Si:P $4\times10^{19}\,\text{cm}^{-3}$ and $2\times10^{20}\,\text{cm}^{-3}$, we observe quantum interference and use the extracted gate coupling to determine the dominant energy scale and the corresponding mean-free paths. For the higher doped device the analysis yields a mean free path of $4\pm2\,\text{nm}$, which is on the order of the average dopant spacing and suggests scattering on unactivated or activated dopants. For the device with an activated dopant density of $4\times10^{19}\,\text{cm}^{-3}$ the quantum interference effects suggest a mean free path of $10\pm2\,\text{nm}$, which is comparable to the nanowire width, and thus quasi-ballistic transport. A temperature dependent analysis of Universal Conductance Fluctuations suggests a coherence length above the nanowire length for temperatures below 1.9 K and decoherence from 1D electron-electron interactions for higher temperatures. The mobility is limited by scattering on impurities rather than the expected surface roughness scattering for nanowires with diameters larger or comparable to the Fermi wavelength. Our measurements therefore provide insight into the performance limitations from dominant scattering and dephasing mechanisms in technologically relevant silicon device geometries.

cond-mat.mes-hall↗

arXiv2018

Spiro-Conjugated Molecular Junctions: between Jahn-Teller Distortion and Destructive Quantum Interference

The quest for molecular structures exhibiting strong quantum interference effects in the transport setting has long been on the forefront of chemical research. Here, we establish theoretically that the unusual geometry of spiro-conjugated systems gives rise to complete destructive interference in the resonant-transport regime. This results in a current blockade of the type not present in meta-connected benzene or similar molecular structures. We further show that these systems can undergo a transport-driven Jahn-Teller distortion which can lift the aforementioned destructive-interference effects. The overall transport characteristics is determined by the interplay between the two phenomena. Spiro-conjugated systems may therefore serve as a novel platform for investigations of quantum interference and vibronic effects in the charge transport setting. The potential to control quantum interference in these systems can also turn them into attractive components in designing functional molecular circuits.

cond-mat.mes-hall↗

arXiv2017

Field-Effect Control of Graphene-Fullerene Thermoelectric Nanodevices

Although it was demonstrated that discrete molecular levels determine the sign and magnitude of the thermoelectric effect in single-molecule junctions, full electrostatic control of these levels has not been achieved to date. Here, we show that graphene nanogaps combined with gold microheaters serve as a testbed for studying single-molecule thermoelectricity. Reduced screening of the gate electric field compared to conventional metal electrodes allows control of the position of the dominant transport orbital by hundreds of meV. We find that the power factor of graphene-fullerene junctions can be tuned over several orders of magnitude to a value close to the theoretical limit of an isolated Breit-Wigner resonance. Furthermore, our data suggest that the power factor of an isolated level is only given by the tunnel coupling to the leads and temperature. These results open up new avenues for exploring thermoelectricity and charge transport in individual molecules and highlight the importance of level alignment and coupling to the electrodes for optimum energy conversion in organic thermoelectric materials.

cond-mat.mes-hall↗

arXiv2017

Environment-Assisted Quantum Transport through Single-Molecule Junctions

Single-molecule electronics has been envisioned as the ultimate goal in the miniaturisation of electronic circuits. While the aim of incorporating single-molecule junctions into modern technology still proves elusive, recent developments in this field have begun to enable experimental investigation fundamental concepts within the area of chemical physics. One such phenomenon is the concept of Environment-Assisted Quantum Transport which has emerged from the investigation of exciton transport in photosynthetic complexes. Here, we study charge transport through a two-site molecular junction coupled to a vibrational environment. We demonstrate that vibrational interactions can also significantly enhance the current through specific molecular orbitals. Our study offers a clear pathway towards finding and identifying environment-assisted transport phenomena in charge transport settings.

cond-mat.mes-hall↗