Charge Tunneling Research Articles

Regulating the π-π interaction with shortened electron tunneling distance for efficient charge storage

Coupling organic redox moieties with carbon through π–π interaction is a widely used strategy to boost the energy densities of electrochemical capacitors, but the low electron tunneling probability of π–π interaction through the out-of-plane direction intrinsically limits the charge storage capacity and rate capability. Here we rationally construct B involved functional sites on the surface of porous carbon fibers for coupling hydroquinone (HQ) molecules with enhanced π–π interaction, which enables exceptional charge storage performance by regulating the interfacial charge tunneling behavior. The designed HQ-carbon composites deliver an attractive areal capacitance of 2.68 F cm−2 at 2 mA cm−2 and retain 2.10 F cm−2 at 40 mA cm−2, representing the highest areal capacitance among the ever-reported organic redox moiety/carbon systems. Meanwhile, maximum volume energy density and power density of 12.2 mWh cm−3 and 3683 mW cm−3 are demonstrated by assembling an asymmetric supercapacitor with Ti3C2Tx. The theoretical calculation indicates the decreased tunneling distance originating from the regulated π–π interaction contributes to the fast kinetics of proton-involved charge-storage process. The capability of regulating the charge transfer behavior offers a new vision to couple organic redox moieties with carbon for energy storage and beyond.

Tunnel magnetodielectric effect: Theory and experiment

The recently discovered tunnel magnetodielectric (TMD) effect—the magnetic field-induced increase in the dielectric permittivity (ε′) of nanogranular composites caused by the spin-dependent quantum mechanical charge tunneling—is of interest for both the scientific value that combines the fields of magnetoelectric and spintronics and multifunctional device applications. However, little is known about how large the maximum dielectric change Δε′/ε′ can achieve and why the Δε′/ε′ variations obey the dependence of square of normalized magnetization (m2), which are critically important for searching and designing materials with higher Δε′/ε′. Here, we perform approximate theoretical derivation and reveal that the maximum Δε′/ε′ can be estimated using intrinsic tunneling spin polarization (PT) and extrinsic normalized magnetization (m), that is, Δε′/ε′ = 2PT2m2. This formulation allows predicting over 200% of theoretical limit for m = 1 and accounts for the observed m2 dependence of Δε′/ε′ for a given PT. We experimentally demonstrate that x-dependence of Δε′/ε′ in (CoxFe100−x)–MgF2 films is phenomenologically consistent with this formulation. This work is pivotal to the design of ultra-highly tunable magnetoelectric applications of the TMD effect at room temperature.

A superconductor free of quasiparticles for seconds

Superconducting devices, based on the Cooper pairing of electrons, play an important role in existing and emergent technologies, ranging from radiation detectors to quantum computers. Their performance is limited by spurious quasiparticle excitations formed from broken Cooper pairs. Efforts to achieve ultra-low quasiparticle densities have reached time-averaged numbers of excitations on the order of one in state-of-the-art devices. However, the dynamics of the quasiparticle population as well as the time scales for adding and removing individual excitations remain largely unexplored. Here, we experimentally demonstrate a superconductor completely free of quasiparticles for periods lasting up to seconds. We monitor the quasiparticle number on a mesoscopic superconductor in real time by measuring the charge tunneling to a normal metal contact. Quiet, excitation-free periods are interrupted by random-in-time Cooper pair breaking events, followed by a burst of charge tunneling within a millisecond. Our results demonstrate the possibility of operating devices without quasiparticles with potentially improved performance. In addition, our experiment probes the origins of nonequilibrium quasiparticles in our device; the decay of the Cooper pair breaking rate over several weeks following the initial cooldown rules out processes arising from cosmic or long-lived radioactive sources.

Ion‐Accumulation‐Induced Charge Tunneling for High Gain Factor in P–I–N‐Structured Perovskite CH3NH3PbI3 X‐Ray Detector

AbstractLead halide perovskite‐based X‐ray detectors show very promising sensitivity and low detection limit, which can be used for next‐generation, room‐temperature radiation detections. It is interesting to find that the diode‐structured X‐ray detector shows very high photocurrent gain under small reversed bias voltage, which is unusual and should be investigated and understood for better device design. In this regard, a lead halide perovskite‐based X‐ray detector with the p–i–n structure is fabricated and studied. The p–i–n structured device shows abnormal and excellent photoconductor properties with high photocurrent gain factor under reverse bias. Further device simulation reveals that the ion migration and accumulation in the perovskite material are responsible for the large band‐bending at the interface, which may induce charge tunneling to reduce the contact resistance and causes the reverse‐biased device to work as a photoconductor rather than a photodiode. This finding provides a new approach to the understanding and design of high‐performance X‐ray detectors utilizing ionic semiconductors like lead halide perovskites.

Volatility Transition from Short‐Term to Long‐Term Photonic Transistor Memory by Using Smectic Liquid Crystalline Molecules as a Floating Gate

AbstractRod‐like molecules with liquid crystalline phase transitions show highly ordered stacking and orientation, which is promising as the floating gate electret in high‐performance photonic field‐effect transistor (FET) memory. In this work, a series of rod‐like molecules, alkyl‐dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (Cn‐DNTT), are investigated with a smectic liquid crystalline phase transition. The photonic FET memory featuring these rod‐like molecules is correlated with their morphology and crystallographic properties. A volatility transition from short−term to long−term memory behavior is found by utilizing the smectic liquid crystalline phase transitions (SmX, X = H, K, E) to orient the stacking in the floating gate. Accordingly, the annealed 2,9‐didecyldinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (C10‐DNTT) polycrystalline film with the optimized alkyl chain length achieved preferential end‐on orientation associated with the herringbone‐type stacking to store charges during photowriting, along with effective charge tunneling for the trapped charges during electrical erasing. Therefore, the resultant photonic FET memory provided a superior ON/OFF current ratio of up to 105 with retention of 104 after 104 s. The results demonstrate that rod‐like molecules with smectic liquid crystalline phase and highly ordered orientation have great potentials for developing high‐performance photonic FET memory.

Thermally Stable All‐Perovskite Tandem Solar Cells Fully Using Metal Oxide Charge Transport Layers and Tunnel Junction

All‐perovskite tandem solar cells offer a promising avenue to go beyond the efficiency limit of single‐junction devices. Their efficiencies have been increasing rapidly in the past few years; however, their commercial viability is hindered by the instability under thermal stressing. Herein, comprehensive device design strategies are proposed to achieve thermally stable all‐perovskite tandem solar cells while retaining the advantages of solution processing. Metal oxides, i.e., NiOx and SnO2, are used for the hole and electron transport layers in both wide bandgap and narrow subcells. The metal‐based recombination layer is replaced with a stable and conductive indium tin oxide nanocrystals film to fabricate an all metal‐oxide‐based tunnel junction. Based on those design strategies, the encapsulated all‐perovskite tandem solar cells retained 85% of their initial efficiency after stressing at 85 °C for 2500 h and maintained >80% of their initial performance after 900 h operation at the maximum power point and operating temperature of ≈65 °C. Achieving such thermal stability represents a crucial step toward commercial viability of all‐perovskite tandem solar cells.

Splitting of the energy spectrum of an indirect exciton upon electron tunnelling between nanoparticles

We report an analytical study of the splitting of the energy spectrum of an electron for a quasi-two-dimensional indirect exciton (Q2D-IX) localised at the ‘dielectric nanoparticle–dielectric medium’ interface. The splitting results from electron tunnelling through a potential barrier separating neighbouring nanoparticles. The obtained expressions determine the energy and spatial parameters of the probability of electron tunnelling and the value of the energy splitting. It is found that tunnelling is possible under rigid conditions for the spatial parameters of the nanosystem and the ratio of the energies of the excited and ground exciton states. Tunnelling-induced splitting of the electron energy can reach 0.1 eV for some dielectric structures. This allows the impact of charge tunnelling on the energy spectrum of Q2D-IX systems to be predicted.

Statistical detection of Josephson, Andreev, and single quasiparticle currents in scanning tunneling microscopy

We present a method to identify distinct tunneling modes in a tunable superconducting tunnel junction composed of a superconducting tip and a sample in a scanning tunneling microscope. Combining the relative decay constant of tunneling current extracted from $I\ensuremath{-}V\ensuremath{-}z$ spectroscopy with its statistical analysis over the atomic disorders in the sample surface, we identified the crossover of dominant tunneling modes between single charge tunneling, Andreev reflection (AR), and Josephson tunneling with respect to the bias voltage at a measurement temperature nearly half of the critical temperature. The method enables one to determine the specific tunneling regime independently of the spectral shapes and to reveal intrinsic modulation of AR and Josephson current by disorder that will be crucial for superconducting quantum information processing.

Molecular Conformation in Charge Tunneling across Large-Area Junctions.

Self-assembled monolayers are predicated on thermodynamic equilibrium; hence, their properties project accessible relaxation pathways. Herein, we demonstrate that charge tunneling correlates with conformational degrees of freedom(s). Results from open chain and cyclic head groups show that, as expected, distribution in tunneling data correlates with the orientation of the head group, akin to the odd-even effect and more importantly the degree of conformational freedom, but fluctuates with applied bias. Trends in nature of distributions in current density illuminate the need for higher statistical moments in understanding these rather dynamic systems. We employ skewness, kurtosis, and estimation plots to show that the conformational degree of freedom in the head group significantly amplifies the odd-even effect and may lead to enhanced or perturbed tunneling based on whether the head group is on an odd- or even-parity spacer.

C-axis aligned crystalline indium-gallium-zinc oxide (CAAC-IGZO) and high-k charge trapping film for flash memory application

C-axis aligned crystalline indium-gallium-zinc oxide (CAAC-IGZO) was obtained using tantalum (Ta) induced crystallization with appropriate post-annealing and applied as a channel of the thin film transistor (TFT) flash memory device. Atomic layer deposited Al2O3, HfO2, and Al2O3 thin films were used for the blocking layer (BL), charge trap layer (CTL) and tunneling layer (TL), respectively. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) analysis show the formation of a CAAC-IGZO layer with a (009) peak on the c-axis. Compared with a device using amorphous IGZO (a-IGZO) material as a channel, a device using CAAC-IGZO as a channel material shows improved transistor characteristics with low threshold voltage, low subthreshold swing, high field effect mobility, and high on-current to off-current ratio (ION/OFF). In the program/erase (P/E) characterization, CAAC-IGZO channel device (ΔVTH = 1.0 V) has a larger memory window than a-IGZO channel device (ΔVTH = 0.5 V). The retention and endurance characteristics of the CAAC-IGZO device were obtained up to 104 s and 103 cycles, respectively, without any noticeable degradation. It is believed that the proposed CAAC-IGZO material could be considered as an alternative to the poly-Si material having defects due to the grain-boundaries.

Tracking Electron Dynamics of Single Molecules in Scanning Tunneling Microscopy Junctions with Laser Pulses.

On the basis of real-time simulations, we devise a method to extend the capability of scanning tunneling microscopy (STM) to track the electronic dynamics of molecules on a material's surface with the ultrafast temporal resolution of laser pulses. The intrinsic mechanism of visualization of electronic dynamics by measuring tunneling charge is attributed to the interference between the electronic oscillations stimulated by pump and probe pulses. The charge-transfer rate from molecule to the surrounding environment can be estimated with the decay time of electronic dynamics, which can also be detected by measuring the tunneling charge across the STM junction. Moreover, it is found that the tunneling charge can be varied precisely by changing the carrier-envelope phase (CEP) of the pulses, and this phase-dependence of tunnelling diminishes as the duration of incident laser pulses increases. The proposed scheme provides an alternative means for visualization of electron dynamics of single molecules by measuring tunnelling charges.

Highly Efficient Experimental Approach to Evaluate Metal to 2D Semiconductor Interfaces in Vertical Diodes with Asymmetric Metal Contacts.

The energy band alignments and associated material properties at the contacts between metal and two-dimensional (2D) semiconducting transition metal dichalcogenide (SCTMD) films determine the important traits in 2D SCTMD-based electronic and optical device applications. In this work, we realize 2D vertical diodes with asymmetric metal-SCTMD contact areas where currents are dominated by the contact-limited charge flows in the transport regimes of Fowler-Nordheim tunneling and Schottky emission. With straightforward current-voltage characteristics, we can accurately evaluate the interface parameters such as Schottky barrier heights and the vertical effective masses of tunneling charges. In particular, the differing contact areas and resultant current rectifications allow us to address specific Schottky barrier locations with respect to the conduction and valence band edges of 2D semiconducting WSe2, WS2, MoSe2, and MoS2, thereby determining whether p-type holes or n-type electrons become the majority charge carriers in the SCTMD devices. We demonstrate that our experimental and analytical approaches can be utilized as a simple but powerful material metrology to qualitatively and quantitatively evaluate various metal-SCTMD contacts.

Electron tunneling through interim ligand layers towards photoredox selective organic transformation

Photocatalytic selective organic transformation represents an emerging avenue for artificial photosynthesis toward renewable solar energy conversion. However, solar-to-chemical conversion efficiency in photocatalysis is largely hampered by the sluggish charge transfer kinetic and difficulty in precise control over the charge migration pathway. Herein, we demonstrate conceptually new metal–insulator–semiconductor (MIS) electron tunneling photosystems to finely modulate the directional charge flow for photoredox selective organic transformation. The ultrathin insulating organic ligands layers capped on the surfaces of metal nanocrystals (NYs) and transition metal chalcogenides quantum dots (TMCs QDs) mutually function as precise directing-mediums to stimulate spontaneous electrostatic self-assembly between the tailor-made oppositely charged metal NYs and TMCs QDs for constructing metal (Au, Pd) NYs/TMCs (CdSe, CdS) QDs heterostructured electron tunneling photosystems. The electrons photoexcited from TMCs QDs can be efficaciously extracted and tunneled to metal NYs across the intermediate insulating hierarchical ligands layers to participate in the photoredox catalysis. The metal NYs-insulating ligands-TMCs QDs photosystems can efficiently mediate the minority carrier transport across the intermediate insulating ligand layers with minimal recombination, thereby resulting in the significantly enhanced net efficiency of multifarious photoactivities toward selective organic transformation including anaerobic photoreduction of nitroaromatics to amino derivatives and selective photo-oxidation of aromatic alcohols to aldehydes under visible light irradiation. The ligand-triggered electron tunneling effect has been evidence to be universal. Our work would inspire ongoing interest in exploring diverse organic ligands-based charge tunneling photosystems and provide a valuable roadmap for substantial solar energy conversion.

Fractional Coulomb blockade for quasi-particle tunneling between edge channels.

In the fractional quantum Hall effect, the elementary excitations are quasi-particles with fractional charges as predicted by theory and demonstrated by noise and interference experiments. We observe Coulomb blockade of fractional charges in the measured magneto-conductance of a 1.4-micron-wide quantum dot. Interaction-driven edge reconstruction separates the dot into concentric compressible regions with fractionally charged excitations and incompressible regions acting as tunnel barriers for quasi-particles. Our data show the formation of incompressible regions of filling factors 2/3 and 1/3. Comparing data at fractional filling factors to filling factor 2, we extract the fractional quasi-particle charge e */e = 0.32 ± 0.03 and 0.35 ± 0.05. Our investigations extend and complement quantum Hall Fabry-Pérot interference experiments investigating the nature of anyonic fractional quasi-particles.

Tunneling current modulation in atomically precise graphene nanoribbon heterojunctions

Lateral heterojunctions of atomically precise graphene nanoribbons (GNRs) hold promise for applications in nanotechnology, yet their charge transport and most of the spectroscopic properties have not been investigated. Here, we synthesize a monolayer of multiple aligned heterojunctions consisting of quasi-metallic and wide-bandgap GNRs, and report characterization by scanning tunneling microscopy, angle-resolved photoemission, Raman spectroscopy, and charge transport. Comprehensive transport measurements as a function of bias and gate voltages, channel length, and temperature reveal that charge transport is dictated by tunneling through the potential barriers formed by wide-bandgap GNR segments. The current-voltage characteristics are in agreement with calculations of tunneling conductance through asymmetric barriers. We fabricate a GNR heterojunctions based sensor and demonstrate greatly improved sensitivity to adsorbates compared to graphene based sensors. This is achieved via modulation of the GNR heterojunction tunneling barriers by adsorbates.

Characterizing Chelation at Surfaces by Charge Tunneling.

This paper describes a surface analysis technique that uses the "EGaIn junction" to measure tunneling current densities (J(V), amps/cm2) through self-assembled monolayers (SAMs) terminated in a chelating group and incorporating different transition metal ions. Comparisons of J(V) measurements between bare chelating groups and chelates are used to characterize the composition of the SAM and infer the dissociation constant (Kd, mol/L), as well as kinetic rate constants (koff, L/mol·s; kon, 1/s) of the reversible chelate-metal reaction. To demonstrate the concept, SAMs of 11-(4-methyl-2,2'-bipyrid-4'-yl (bpy))undecanethiol (HS(CH2)11bpy) were incubated within ethanol solutions of metal salts. After rinsing and drying the surface, measurements of current as a function of incubation time and concentration in solution are used to infer koff, kon, and Kd. X-ray photoelectron spectroscopy (XPS) provides an independent measure of surface composition to confirm inferences from J(V) measurements. Our experiments establish that (i) bound metal ions are stable to the rinsing step as long as the rinsing time, τrinse ≪ ; (ii) the bound metal ions increase the current density at the negative bias and reduce the rectification observed with free bpy terminal groups; (iii) the current density as a function of the concentration of metal ions in solution follows a sigmoidal curve; and (iv) the values of Kd measured using J(V) are comparable to those measured using XPS, but larger than those measured in solution. The EGaIn junction, thus, provides a new tool for the analysis of the composition of the surfaces that undergo reversible chemical reactions with species in solution.

Sequence modulation of tunneling barrier and charge transport across histidine doped oligo-alanine molecular junctions

Series tunneling across peptides composed of various amino acids is one of the main charge transport mechanisms for realizing the function of protein. Histidine, more frequently found in redox active proteins, has been proved to be efficient tunneling mediator. While how it exactly modulates charge transport in a long peptide sequence remains poorly explored. In this work, we studied charge transport of a model peptide junction, where oligo-alanine peptide was doped by histidine at different position, and the series of peptides were self-assembled into a monolayer on gold electrode with soft EGaIn as top electrode to form molecular junction. It was found that histidine increased the overall conductance of the peptide, meanwhile, its position modulated the conductance as well. Quantitative analysis by transport model and ultraviolet photoelectron spectroscopy (UPS) indicated a sequence dependent energy landscape of the tunneling barrier of the junction. Density-functional theory (DFT) calculation on the electronic structure of histidine doped oligo-alanine peptides revealed localized highest occupied molecular orbital (HOMO) on imidazole group of the histidine, which decreased charge transport barrier.

A review on the performance of the underground tunnels against blast loading

The tunneling system has become an important part of the present infrastructure system in all over the world. Therefore, it has become important to ensure the safety of the tunnels against any type of man-made blasting activities or other accidental blasting occurrence. In order to evaluate the performance of the tunnels against blast loading, a detailed review is carried out. Based on the review in the last couple of decades, the various parameters such as tunnel lining materials, tunnel shapes, tunnel lining thickness, tunnel burial depth, charge weight and standoff distance are high influences on the performance of underground tunnels against blast loading. It was observed that the tunnel roof and the tunnel wall center are most vulnerable to the blast loads. Also, it was found that more of the tunnel lining thickness results in lesser deformation at the tunnel roof and the tunnel wall center. The increase in the burial depth of the tunnel would reduce the extent of damage to the tunnel caused by effects of surface blast loading. The stiffness and strength of the ground media may be enhanced against the effects of blast loading by grouting measures. The studies revealed that the lining materials possessing blast waves absorbing properties can be best suited to be used in tunnel linings. Further, it was observed that more damage was caused to the tunnels due to the magnitude of the charge weight. An increase in the blast load causes a significant increase in the fracture area, residual stress and lateral displacement caused to the tunnel by the action of blast load. The standoff distance of the blast load from the tunnel also plays a significant role in the damage of the tunnel. More is the distance between the charge and the tunnel, lesser damage caused to the tunnels. In addition to that, the lining thickness was predicted and the trend was calibrated and fitted logarithmically with the available results. Based on the observation from the literature, it is concluded that the use of a single lining material in the tunnel against blast loading was studied predominantly in the couple of decades. Further, the performance of the tunnels in combination of different tunnel lining materials against blast loading was found limited. The influence of barriers to save the underground tunnels against blast loading was found limited.

Conformation, and Charge Tunneling through Molecules in SAMs.

This paper demonstrates that the molecular conformation (in addition to the composition and structure) of molecules making up self-assembled monolayers (SAMs) influences the rates of charge tunneling (CT) through them, in molecular junctions of the form AuTS/S(CH2)2CONR1R2//Ga2O3/EGaIn, where R1 and R2 are alkyl chains of different length. The lengths of chains R1 and R2 were selected to influence the conformations and conformational homogeneity of the molecules in the monolayer. The conformations of the molecules influence the thickness of the monolayer (i.e. tunneling barrier width) and their rectification ratios at ±1.0 V. When R1 = H, the molecules are well ordered and exist predominantly in trans-extended conformations. When R1 is an alkyl group (e.g., R1 ≠ H), however, their conformations can no longer be all-trans-extended, and the molecules adopt more gauche dihedral angles. This change in the type of conformation decreases the conformational order and influences the rates of tunneling. When R1 = R2, the rates of CT decrease (up to 6.3×), relative to rates of CT observed through SAMs having the same total chain lengths, or thicknesses, when R1 = H. When R1 ≠ H ≠ R2, there is a weaker correlation (relative to that when R1 = H or R1 = R2) between current density and chain length or monolayer thickness, and in some cases the rates of CT through SAMs made from molecules with different R2 groups are different, even when the thicknesses of the SAMs (as determined by XPS) are the same. These results indicate that the thickness of a monolayer composed of insulating, amide-containing alkanethiols does not solely determine the rate of CT, and rates of charge tunneling are influenced by the conformation of the molecules making up the junction.

Carbon Monoxide Oxidation over Gold Nanoparticles Deposited onto Alumina Film Grown on Mo(110) Substrate: An Effect of Charge Tunneling through the Oxide Film.

Formation of gold nanosized particles supported by aluminum oxide film grown on Mo(110) substrate and oxidation of carbon monoxide molecules on their surface have been in-situ studied in ultra-high vacuum by means of Auger electron spectroscopy (AES), reflection-absorption infrared spectroscopy (RAIRS), low energy electron diffraction (LEED), atomic force microscopy (AFM), temperature-programmed desorption (TPD), and work function measurements. The main focus was to follow how the thickness of the alumina film influences the efficiency of CO oxidation in an attempt to find out evidence of the possible effect of electron tunneling between the metal substrate and the Au particle through the oxide interlayer. Providing the largest degree of surface identity of the studied metal/oxide system at different thicknesses of the alumina film (two, four, six, and eight monolayers), it was found that the CO oxidation efficiency, defined as CO2 to CO TPD peaks intensity ratio, exponentially decays with the oxide film thickness growth. Taking into account the known fact that the CO oxidation efficiency depends on the amount of excess charge acquired by Au particle, the latter suggests that electron tunneling adds efficiency to the oxidation process, although not significantly.