Sub-1K Cold-Electron Quantum Well Switching at Room Temperature.

Quantum states can provide means to systematically manipulate the transport of electrons. Here we present electron transport across quasi-bound states of two heterogeneous quantum wells (QWs), where the transport of thermally excited electrons is blocked or enabled depending on the relative positions of the two quasi-bound states, with an abrupt current onset occurring when the two QW states align. The QW switch comprises a source (Cr), QW1 (Cr2O3), QW2 (SnOx, x < 2), a tunneling barrier (SiO2), and a drain (Si), where the effective electron mass of QW1 (m*QW1) is selected to be larger than QW2 (m*QW2). The current-voltage (I-V) measurements of the fabricated devices show abrupt current onsets, with the current transition occurring within 0.25 mV, corresponding to an effective electron temperature of 0.8 K at room temperature. Since transistor power consumption is fundamentally tied to effective electron temperature, this sub-1K cold-electron QW switching holds promise for highly energy-efficient computing.

Structural Manipulation of Spin Excitations in a Molecular Junction.

Single metallocene molecules act as sensitive spin detectors when decorating the probe of a scanning tunneling microscope (STM). However, the impact of the atomic-scale electrode details on the molecular spin state has remained elusive to date. Here, a nickelocene (Nc) STM junction is manipulated in an atomwise manner showing clearly the dependence of the spin excitation spectrum on the anchoring of Nc to Cu(111), a Cu monomer, and trimer. Moreover, while the spin state of the same Nc tip is a triplet with tunable spin excitation energies upon contacting the surface, it transitions to a Kondo-screened doublet on a Cu atom. Notably, the nontrivial magnetic exchange interaction of the molecular spin with the electron continuum of the substrate determines the spectral line shape of the spin excitations.

Entrapment and Reactivation of Polysulfides in Conductive Amphiphilic Covalent Organic Frameworks Enabling Superior Capacity and Stability of Lithium-Sulfur Batteries.

Inhibiting the shuttle of polysulfides is of great significance for promoting the practical application of lithium-sulfur batteries (LSBs). Here, an imine-linked covalent organic framework@carbon nanotube (COF@CNT) interlayer composed of triazine and boroxine rings is constructed between the sulfur cathode and the separator for polysulfides reception and reutilization. The introduction of CNT imparts the conductor characteristic to the interlayer attributed to electron tunneling in thin COF shell, and creates a hierarchical porous architecture for accommodating polysulfides. The uniform distribution of amphiphilic adsorption sites in COF microporous structure not only enables efficient entrapment of polysulfides while allowing the penetration of Li+ ions, but also provides a stable electrocatalytic channel for bidirectional conversion of active sulfur to achieve the substantially improved capacity and stability. The interlayer-incorporated LSBs deliver an ultrahigh capacity of 1446 mA g-1 at 0.1C and an ultralow capacity decay rate of 0.019% at 1C over 1500 cycles. Even at an electrolyte/sulfur ratio of 6 µL mg-1, an outstanding capacity of 995 mAh g-1 and capacity retention of 74.1% over 200 cycles at 0.2C are obtained. This work offers a compelling polysulfides entrapment and reactivation strategy for stimulating the study on ultra-stable LSBs.

Revealing the Properties of Electrically Driven Optical Antennas via Conductive Atomic Force Microscope.

Light emission from ultracompact electrically driven optical antennas (EDOAs) has garnered significant attention due to its terahertz modulation bandwidth. Typically, the EDOAs are fixed and nonadjustable once fabricated, thus hindering the attempts to investigate the influence of structural geometry on light emission properties. Here, we propose and demonstrate that the EDOAs can be constructed by carefully manipulating the gold-coated tips of atomic force microscopy operated in conductive mode into contact with the optical antennas covered by insulating film, where the position of the tunnel junction on the antenna surface can be controlled with high accuracy and flexibility. Taking gold nanorod antennas covered by HfO2 film as an example, we found that the highest light generation efficiency is obtained when the tunnel junction is located at the shoulder edge of the nanorod antenna, where the bonding dipolar surface plasmon mode in the junction is spectrally and spatially coupled with the longitudinal radiation mode of the EDOAs. Besides, position variation of the tunnel junction on the nanorod surface also strongly influences the far-field radiation angular distribution and emission spectrum. Numerical simulations are in good agreement with the experimental results. Our findings offer fundamental insights into the influence of structural parameters on the light emission performance of EDOAs, thus leading to better design of EDOAs with high light generation efficiency and powerful functionality.

Atomic-Resolution Vibrational Mapping of Bilayer Borophene.

The successful synthesis of borophene beyond the monolayer limit has expanded the family of two-dimensional boron nanomaterials. While atomic-resolution topographic imaging has been previously reported, vibrational mapping has the potential to reveal deeper insight into the chemical bonding and electronic properties of bilayer borophene. Herein, inelastic electron tunneling spectroscopy (IETS) is used to resolve the low-energy vibrational and electronic properties of bilayer-α (BL-α) borophene on Ag(111) at the atomic scale. Using a carbon monoxide (CO)-functionalized scanning tunneling microscopy tip, the BL-α borophene IETS spectra reveal unique features compared to single-layer borophene and typical CO vibrations on metal surfaces. Distinct vibrational spectra are further observed for hollow and filled boron hexagons within the BL-α borophene unit cell, providing evidence for interlayer bonding between the constituent borophene layers. These experimental results are compared with density functional theory calculations to elucidate the interplay between the vibrational modes and electronic states in bilayer borophene.

Adaptation processes in Halomicronema hongdechloris, an example of the light-induced optimization of the photosynthetic apparatus on hierarchical time scales.

Oxygenic photosynthesis in Halomicronema hongdechloris, one of a series of cyanobacteria producing red-shifted Chl f, is adapted to varying light conditions by a range of diverse processes acting over largely different time scales. Acclimation to far-red light (FRL) above 700 nm over several days is mirrored by reversible changes in the Chl f content. In several cyanobacteria that undergo FRL photoacclimation, Chl d and Chl f are directly involved in excitation energy transfer in the antenna system, form the primary donor in photosystem I (PSI), and are also involved in electron transfer within photosystem II (PSII), most probably at the ChlD1 position, with efficient charge transfer happening with comparable kinetics to reaction centers containing Chl a. In H. hongdechloris, the formation of Chl f under FRL comes along with slow adaptive proteomic shifts like the rebuilding of the D1 complex on the time scale of days. On shorter time scales, much faster adaptation mechanisms exist involving the phycobilisomes (PBSs), which mainly contain allophycocyanin upon adaptation to FRL. Short illumination with white, blue, or red light leads to reactive oxygen species-driven mobilization of the PBSs on the time scale of seconds, in effect recoupling the PBSs with Chl f-containing PSII to re-establish efficient excitation energy transfer within minutes. In summary, H. hongdechloris reorganizes PSII to act as a molecular heat pump lifting excited states from Chl f to Chl a on the picosecond time scale in combination with a light-driven PBS reorganization acting on the time scale of seconds to minutes depending on the actual light conditions. Thus, structure-function relationships in photosynthetic energy and electron transport in H. hongdechloris including long-term adaptation processes cover 10-12 to 106 seconds, i.e., 18 orders of magnitude in time.

Impact of Single-Melamine Tautomerization on the Excitation of Molecular Vibrations in Inelastic Electron Tunneling Spectroscopy.

Vibrational quanta of melamine and its tautomer are analyzed at the single-molecule level on Cu(100) with inelastic electron tunneling spectroscopy. The on-surface tautomerization gives rise to markedly different low-energy vibrational spectra of the isomers, as evidenced by a shift in mode energies and a variation in inelastic cross sections. Spatially resolved spectroscopy reveals the maximum signal strength on an orbital nodal plane, excluding resonant inelastic tunneling as the mechanism underlying the quantum excitations. Decreasing the probe-molecule separation down to the formation of a chemical bond between the melamine amino group and the Cu apex atom of the tip leads to a quenched vibrational spectrum with different excitation energies. Density functional and electron transport calculations reproduce the experimental findings and show that the shift in the quantum energies applies to internal molecular bending modes. The simulations moreover suggest that the bond formation represents an efficient manner of tautomerizing the molecule.

Steric Effects on Single-Molecule Conductance in Flat-Lying Phenanthrene.

A previous combined experimental and theoretical study found that the position of anchoring groups on a phenanthrene (PHE) backbone played a large role in determining the single-molecule conductance of the PHE derivative. However, a consistent 0.1 G0 feature was found across all PHE derivatives. To understand this, the previously investigated PHE derivatives were placed flat on a simulated Au substrate with a scanning tunneling microscope (STM) tip over PHE and conductance was calculated using the non-equilibrium Green's function technique in conjunction with density functional theory (NEGF-DFT). The location of the tip was varied to find the most conductive and most energetically favorable arrangements, which did not coincide. Furthermore, the variation in conductance found in erect junctions was not present when PHE derivatives were lying flat, with all derivatives calculated to have conductance values around 0.1 G0.

Innovative enhancement of electron tunneling synergy in carbon-doped Ta2O5CuO photocatalyst with nematic liquid crystal for safe drinking water.

This study focuses on enhancing the photocatalytic properties of carbon-doped Ta2O5CuO (C-Ta2O5CuO) nanocomposites for drinking water purification. The nanocomposites were fabricated by depositing C-Ta2O5CuO onto Nematic Liquid Crystal Polaroid (NLCP) obtained from a discarded laptop monitor, employing the sputter deposition method. The X-ray diffraction (XRD) and High-resolution transmission electron microscopy (HRTEM) determined the nanocomposite thin films' crystallinity and structural properties. The EDX and XPS analyses confirmed the elemental composition and reality of the Cu-incorporated Ta2O5 nanocomposites, respectively. The combination of electron tunneling enhancement provided by the NLCP and graphitic carbon led to exceptional photocatalytic performance. This was particularly evident in the efficient degradation of P-Rosaniline Hydrochloride (PRH) dye in an aqueous medium. C-Ta2O5CuO catalytic activities were estimated at various dye concentrations, repeatability, reusability with time, and kinetics. Coating's stability and long-term activity in photocatalysis reactions were also tested. Additionally, Cu present in the C-Ta2O5CuO and ˙OH radicals exhibited remarkable bactericidal activity. They displayed significant antibacterial efficacy against both gram-positive Escherichia coli (E. coli) and gram-negative Staphylococcus aureus (S. aureus) bacteria. These findings have significant implications for the development of advanced materials with potent photocatalytic and antibacterial properties, holding promise for improving drinking water quality and addressing environmental and health challenges.

How electron tunneling and uphill excitation energy transfer support photochemistry in Halomicronema hongdechloris.

Halomicronema hongdechloris, the first cyanobacterium reported to produce the red-shifted chlorophyll f (Chl f) upon acclimation to far-red light, demonstrates remarkable adaptability to diverse light conditions. The photosystem II (PS II) of this organism undergoes reversible changes in its Chl f content, ranging from practically zero under white-light culture conditions to a Chl f: Chl a ratio of up to 1:8 when exposed to far-red light (FRL) of 720-730 nm for several days. Our ps time- and wavelength-resolved fluorescence data obtained after excitation of living H. hongdechloris cells indicate that the Soret band of a far-red (FR) chlorophyll involved in charge separation absorbs around 470 nm. At 10 K, the fluorescence decay at 715-720 nm is still fast with a time constant of 165 ps indicating an efficient electron tunneling process. There is efficient excitation energy transfer (EET) from 715-720 nm to 745 nm with the latter resulting from FR Chl f, which mainly functions as light-harvesting pigment upon adaptation to FRL. From there, excitation energy reaches the primary donor in the reaction center of PS II with an energetic uphill EET mechanism inducing charge transfer. The fluorescence data are well explained with a secondary donor PD1 represented by a red-shifted Chl a molecule with characteristic fluorescence around 715 nm and a more red-shifted FR Chl f with fluorescence around 725 nm as primary donor at the ChlD1 or PD2 position.

Light-Emitting Plasmonic Tunneling Junctions: Current Status and Perspectives.

Quantum tunneling, in which electrons can tunnel through a finite potential barrier while simultaneously interacting with other matter excitation, is one of the most fascinating phenomena without classical correspondence. In an extremely thin metallic nanogap, the deep-subwavelength-confined plasmon modes can be directly excited by the inelastically tunneling electrons driven by an externally applied voltage. Light emission via inelastic tunneling possesses a great potential application for next-generation light sources, with great superiority of ultracompact integration, large bandwidth, and ultrafast response. In this Perspective, we first briefly introduce the mechanism of plasmon generation in the inelastic electron tunneling process. Then the state of the art in plasmonic tunneling junctions will be reviewed, particularly emphasizing efficiency improvement, precise construction, active control, and electrically driven optical antenna integration. Ultimately, we forecast some promising and critical prospects that require further investigation.

Coulomb blockade and Coulomb staircases in CoBi nanoislands on SrTiO3(001).

We successfully fabricated two-dimensional metallic CoBi nanoislands on SrTiO3(001) substrate by molecular beam epitaxy, and systematically investigated their electronic structures by scanning tunneling microscopy and spectroscopyin situat 4.2 K. Coulomb blockade and Coulomb staircases with discrete and well-separated levels are observed for the individual nanoisland, which is attributed to single-electron tunneling via two tunnel junction barriers. They are in excellent agreement with the simulations based on orthodox theory. Furthermore, we demonstrated that the Coulomb blockade becomes weaker with increasing temperature and almost disappears at ∼22 K in our variable temperature experiment, and its full-width at half-maximum of dI/dVpeaks with temperature is ∼6 mV. Our results provide a new platform for designing single-electron transistors that have potential applications in future microelectronics.

Engineering the Outcoupling Pathways in Plasmonic Tunnel Junctions via Photonic Mode Dispersion for Low-Loss Waveguiding.

Outcoupling of plasmonic modes excited by inelastic electron tunneling (IET) across plasmonic tunnel junctions (TJs) has attracted significant attention due to low operating voltages and fast excitation rates. Achieving selectivity among various outcoupling channels, however, remains a challenging task. Employing nanoscale antennas to enhance the local density of optical states (LDOS) associated with specific outcoupling channels partially addressed the problem, along with the integration of conducting 2D materials into TJs, improving the outcoupling to guided modes with particular momentum. The disadvantage of such methods is that they often involve complex fabrication steps and lack fine-tuning options. Here, we propose an alternative approach by modifying the dielectric medium surrounding TJs. By employing a simple multilayer substrate with a specific permittivity combination for the TJs under study, we show that it is possible to optimize mode selectivity in outcoupling to a plasmonic or a photonic-like mode characterized by distinct cutoff behaviors and propagation length. Theoretical and experimental results obtained with a SiO2-SiN-glass multilayer substrate demonstrate high relative coupling efficiencies of (62.77 ± 1.74)% and (29.07 ± 0.72)% for plasmonic and photonic-like modes, respectively. The figure-of-merit, which quantifies the tradeoff between mode outcoupling and propagation lengths (tens of µm) for both modes, can reach values as high as 180 and 140. The demonstrated approach allows LDOS engineering and customized TJ device performance, which are seamlessly integrated with standard thin film fabrication protocols. Our experimental device is well-suited for integration with silicon nitride photonics platforms.

Exchange Interactions and Intermolecular Hybridization in a Spin-1/2 Nanographene Dimer.

Phenalenyl is a radical nanographene with a triangular shape hosting an unpaired electron with spin S = 1/2. The open-shell nature of the phenalenyl is expected to be retained in covalently bonded networks. As a first step, we report synthesis of the phenalenyl dimer by combining in-solution synthesis and on-surface activation and its characterization on Au(111) and on a NaCl decoupling layer by means of inelastic electron tunneling spectroscopy (IETS). IETS shows inelastic steps that are identified as singlet-triplet excitation arising from interphenalenyl exchange. Spin excitation energies with and without the NaCl decoupling layer are 48 and 41 meV, respectively, indicating significant renormalization due to exchange with Au(111) electrons. Furthermore, third-neighbor hopping-induced interphenalenyl hybridization is fundamental to explaining the position-dependent bias asymmetry of the inelastic steps and activation of kinetic interphenalenyl exchange. Our results pave the way for bottom-up synthesis of S = 1/2 spin-lattices with large exchange interactions.

Probing the Inelastic Electron Tunneling via the Photocurrent in a Vertical Graphene van der Waals Heterostructure.

Inelastic electron tunneling (IET), accompanied by energy transfer between the tunneling charge carriers and other elementary excitations, is widely used to investigate the collective modes and quasiparticles in solid-state materials. In general, the inelastic contribution to the tunneling current is small compared to the elastic part and is therefore only prominent in the second derivative of the tunneling current with respect to the bias voltage. Here we demonstrate a direct observation of the IET by measuring the photoresponse in a graphene-based vertical tunnel junction device. Characteristic peaks/valleys are observed in the bias-voltage-dependent tunneling photocurrent at low temperatures, which barely shift with the gate voltage applied to graphene and diminish gradually as the temperature increases. By comparing with the second-order differential conductance spectra, we establish that these features are associated with the phonon-assisted IET. A simple model based on the photoexcited hot-carrier tunneling in graphene qualitatively explains the response. Our study points to a promising means of probing the low-energy elementary excitations utilizing the graphene-based van der Waals (vdW) heterostructures.

Coenzyme Q10 trapping in mitochondrial complex I underlies Leber's hereditary optic neuropathy.

How does a single amino acid mutation occurring in the blinding disease, Leber's hereditary optic neuropathy (LHON), impair electron shuttling in mitochondria? We investigated changes induced by the m.3460 G>A mutation in mitochondrial protein ND1 using the tools of Molecular Dynamics and Free Energy Perturbation simulations, with the goal of determining the mechanism by which this mutation affects mitochondrial function. A recent analysis suggested that the mutation's replacement of alanine A52 with a threonine perturbs the stability of a region where binding of the electron shuttling protein, Coenzyme Q10, occurs. We found two functionally opposing changes involving the role of Coenzyme Q10. The first showed that quantum electron transfer from the terminal Fe/S complex, N2, to the Coenzyme Q10 headgroup, docked in its binding pocket, is enhanced. However, this positive adjustment is overshadowed by our finding that the mobility of Coenzyme Q10 in its oxidized and reduced states, entering and exiting its binding pocket, is disrupted by the mutation in a manner that leads to conditions promoting the generation of reactive oxygen species. An increase in reactive oxygen species caused by the LHON mutation has been proposed to be responsible for this optic neuropathy.

Single-Charge Tunneling in Codoped Silicon Nanodevices.

Silicon (Si) nano-electronics is advancing towards the end of the Moore's Law, as gate lengths of just a few nanometers have been already reported in state-of-the-art transistors. In the nanostructures that act as channels in transistors or depletion layers in pn diodes, the role of dopants becomes critical, since the transport properties depend on a small number of dopants and/or on their random distribution. Here, we present the possibility of single-charge tunneling in codoped Si nanodevices formed in silicon-on-insulator films, in which both phosphorus (P) donors and boron (B) acceptors are introduced intentionally. For highly doped pn diodes, we report band-to-band tunneling (BTBT) via energy states in the depletion layer. These energy states can be ascribed to quantum dots (QDs) formed by the random distribution of donors and acceptors in such a depletion layer. For nanoscale silicon-on-insulator field-effect transistors (SOI-FETs) doped heavily with P-donors and also counter-doped with B-acceptors, we report current peaks and Coulomb diamonds. These features are ascribed to single-electron tunneling (SET) via QDs in the codoped nanoscale channels. These reports provide new insights for utilizing codoped silicon nanostructures for fundamental applications, in which the interplay between donors and acceptors can enhance the functionalities of the devices.

Granular metals with SiNxdielectrics.

Understanding and controlling nanoscale interface phenomena, such as band bending and secondary phase formation, is crucial for electronic device optimization. In granular metal (GM) studies, where metal nanoparticles are embedded in an insulating matrix, the importance of interface phenomena is frequently neglected. We demonstrate that GMs can serve as an exemplar system for evaluating the role of secondary phases at interfaces through a combination of x-ray photoemission spectroscopy (XPS) and electrical transport studies. We investigated SiNxas an alternative to more commonly used oxide-insulators, as SiNx-based GMs may enable high temperature applications when paired with refractory metals. Comparing Co-SiNxand Mo-SiNxGMs, we found that, in the tunneling-dominated insulating regime, Mo-SiNxhad reduced metal-silicide formation and orders-of-magnitude lower conductivity. XPS measurements indicate that metal-silicide and metal-nitride formation are mitigatable concerns in Mo-SiNx. Given the metal-oxide formation seen in other GMs, SiNxis an appealing alternative for metals that readily oxidize. Furthermore, SiNxprovides a path to metal-nitride nanostructures, potentially useful for various applications in plasmonics, optics, and sensing.

Transport Characteristics of Silicon Multi-Quantum-Dot Transistor Analyzed by Means of Experimental Parametrization Based on Single-Hole Tunneling Model.

The transport characteristics of a gate-all-around Si multiple-quantum-dot (QD) transistor were studied by means of experimental parametrization using theoretical models. The device was fabricated by using the e-beam lithographically patterned Si nanowire channel, in which the ultrasmall QDs were self-created along the Si nanowire due to its volumetric undulation. Owing to the large quantum-level spacings of the self-formed ultrasmall QDs, the device clearly exhibited both Coulomb blockade oscillation (CBO) and negative differential conductance (NDC) characteristics at room temperature. Furthermore, it was also observed that both CBO and NDC could evolve along the extended blockade region within wide gate and drain bias voltage ranges. By analyzing the experimental device parameters using the simple theoretical single-hole-tunneling models, the fabricated QD transistor was confirmed as comprising the double-dot system. Consequently, based on the analytical energy-band diagram, we found that the formation of ultrasmall QDs with imbalanced energetic natures (i.e., imbalanced quantum energy states and their imbalanced capacitive-coupling strengths between the two dots) could lead to effective CBO/NDC evolution in wide bias voltage ranges.

Single-Molecule Continuous-Wave Terahertz Rectification Spectroscopy and Microscopy.

We report rectification spectroscopy (RS) for single molecules performed with continuous-wave terahertz (CW THz) radiation at the tunneling junction of a scanning tunneling microscope (STM) at 8 K. CW THz-RS serves as a new technique in single-molecule vibrational and magnetic excitation spectroscopy besides inelastic electron tunneling spectroscopy (IETS). By quantitatively studying IETS and THz RS, we show that CW THz induces a sinusoidal bias modulation with amplitude linearly dependent on the THz far-field amplitude. Such THz-induced bias modulation amplitude appears to be sensitive to the THz beam alignment but insensitive to variation in the tunneling gap far smaller than the THz wavelength.