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Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating ultra-thin thermal metamaterials based on crystalline lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m^2K/GW) and ultralow cross-plane thermal conductivities (0.01-0.07 Wm^-1K^-1) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics., Comment: 25 page 4 figures

The final performance of a molecular electronic device is determined by the chemical structure of the molecular wires used in its assembly. Molecular place-exchange was used to incorporate di-thioacetate terminated molecules into ordered arrays of dodecanethiol capped gold nanoparticles. X-ray photoelectron spectroscopy confirmed successful molecular replacement. Room-temperature molecular conductance of a statistically large number of devices reveals that conductance is enhanced by up to two orders of magnitude for the di-thioacetate terminated molecules. Density functional theory transport calculations were performed on five different configurations of the di-thioacetate molecules between gold electrodes, and the calculated average conductance values are in good agreement with the conductance experimentally-observed trend. Our findings highlight important cooperative effects of bridging neighboring gold nanoparticles and choice of appropriate molecular wires when designing devices for efficient transport.

Novel organic materials formed from functional molecules are attractive for various nanoelectronic applications because they are environmentally friendly, widely available and inexpensive. Recent advancement in bottom-up fabrication methods has made it possible to design and synthesis functional molecules with desired functionalities and engineer their properties precisely. This requires deeper understanding of if the properties of building blocks e.g. single molecules can be translated to many molecule junctions in the form of self-assembled monolayers (SAM). Therefore, understanding the effect of intermolecular interaction becomes important. In this paper, we study the effect of intermolecular interactions on the charge transport and thermoelectric properties of junctions formed by parallel molecules between metallic electrodes. We demonstrate that the electrical conductance and Seebeck coefficient are enhanced simultaneously leading to more than an order of magnitude enhancement of power factor as a result of intermolecular coupling between two molecules of the same kind or different. This strategy can be used to improve the thermoelectric performance of SAMs by engineering their packing density.

Atomically precise graphene nanoribbons (GNRs) are increasingly attracting interest due to their largely modifiable electronic properties, which can be tailored by controlling their width and edge structure during chemical synthesis. In recent years, the exploitation of GNR properties for electronic devices has focused on GNR integration into field-effect-transistor (FET) geometries. However, such FET devices have limited electrostatic tunability due to the presence of a single gate. Here, we report on the device integration of 9-atom wide armchair graphene nanoribbons (9-AGNRs) into a multi-gate FET geometry, consisting of an ultra-narrow finger gate and two side gates. We use high-resolution electron-beam lithography (EBL) for defining finger gates as narrow as 12 nm and combine them with graphene electrodes for contacting the GNRs. Low-temperature transport spectroscopy measurements reveal quantum dot (QD) behavior with rich Coulomb diamond patterns, suggesting that the GNRs form QDs that are connected both in series and in parallel. Moreover, we show that the additional gates enable differential tuning of the QDs in the nanojunction, providing the first step towards multi-gate control of GNR-based multi-dot systems.

Bottom-up synthesized graphene nanoribbons (GNRs) are quantum materials that can be structured with atomic precision, providing unprecedented control over their physical properties. Accessing the intrinsic functionality of GNRs for quantum technology applications requires the manipulation of single charges, spins, or photons at the level of an individual GNR. However, experimentally, contacting individual GNRs remains challenging due to their nanometer-sized width and length as well as their high density on the metallic growth substrate. Here, we demonstrate the contacting and electrical characterization of individual GNRs in a multi-gate device architecture using single-walled carbon nanotubes (SWNTs) as ultimately-scaled electrodes. The GNR-SWNT devices exhibit well-defined quantum transport phenomena, including Coulomb blockade, excited states, and Franck-Condon blockade, all characteristics pointing towards the contacting of an individual GNR. Combined with the multi-gate architecture, this contacting method opens a road for the integration of GNRs in quantum devices to exploit their topologically trivial and non-trivial nature.

Graphene nanoribbons (GNRs) have attracted a strong interest from researchers worldwide, as they constitute an emerging class of quantum-designed materials. The major challenges towards their exploitation in electronic applications include reliable contacting, complicated by their small size ($<$50 nm), as well as the preservation of their physical properties upon device integration. In this combined experimental and theoretical study, we report on the quantum dot (QD) behavior of atomically precise GNRs integrated in a device geometry. The devices consist of a film of aligned 5-atoms wide GNRs (5-AGNRs) transferred onto graphene electrodes with a sub 5-nm nanogap. We demonstrate that the narrow-bandgap 5-AGNRs exhibit metal-like behavior resulting in linear IV curves for low bias voltages at room temperature and single-electron transistor behavior for temperatures below 150~K. By performing spectroscopy of the molecular levels at 13~K, we obtain addition energies in the range of 200-300 meV. DFT calculations predict comparable addition energies and reveal the presence of two electronic states within the bandgap of infinite ribbons when the finite length of the 5-AGNRs is accounted for. By demonstrating the preservation of the 5-AGNRs electronic properties upon device integration, as demonstrated by transport spectroscopy, our study provides a critical step forward in the realisation of more exotic GNR-based nano-electronic devices., Comment: 18 pages, 5 figures

If simple guidelines could be established for understanding how quantum interference (QI) can be exploited to control the flow of electricity through single molecules, then new functional molecules, which exploit room-temperature QI could be rapidly identified and subsequently screened. Recently it was demonstrated that conductance ratios of molecules with aromatic cores, with different connectivities to electrodes, can be predicted using a simple and easy-to-use 'magic number theory'. In contrast with counting rules and 'curly-arrow' descriptions of destructive QI, magic number theory captures the many forms of constructive QI, which can occur in molecular cores. Here we address the question of how conductance ratios are affected by electron-electron interactions. We find that due to cancellations of opposing trends, when Coulomb interactions and screening due to electrodes are switched on, conductance ratios are rather resilient. Consequently, qualitative trends in conductance ratios of molecules with extended pi systems can be predicted using simple 'non-interacting' magic number tables, without the need for large-scale computations. On the other hand, for certain connectivities, deviations from non-interacting conductance ratios can be significant and therefore such connectivities are of interest for probing the interplay between Coulomb interactions, connectivity and QI in single-molecule electron transport.

When a single molecule is connected to external electrodes by linker groups, the connectivity of the linkers to the molecular core can be controlled to atomic precision by appropriate chemical synthesis. Recently, the connectivity dependence of the electrical conductance and Seebeck coefficient of single molecules has been investigated both theoretically and experimentally. Here we study the connectivity dependence of the Wigner delay time of single-molecule junctions and the connectivity dependence of superconducting proximity effects, which occur when the external electrodes are replaced by superconductors. Although absolute values of transport properties depend on complex and often uncontrolled details of the coupling between the molecule and electrodes, we demonstrate that ratios of transport properties can be predicted using tables of 'magic numbers,' which capture the connectivity dependence of superconducting proximity effects and Wigner delay times within molecules. These numbers are calculated easily, without the need for large-scale computations. For normal-molecule-superconducting junctions, we find that the electrical conductance is proportional to the fourth power of their magic numbers, whereas for superconducting-molecule-superconducting junctions, the critical current is proportional to the square of their magic numbers. For more conventional normal-molecule-normal junctions, we demonstrate that delay time ratios can be obtained from products of magic number tables.

High electrical conductance molecular nanowires are highly desirable components for future molecular-scale circuitry, but typically molecular wires act as tunnel barriers and their conductance decays exponentially with length. Here we demonstrate that the conductance of fused-oligo-porphyrin nanowires can be either length independent or increase with length at room temperature. We show that this negative attenuation is an intrinsic property of fused-oligo-porphyrin nanowires, but its manifestation depends on the electrode material or anchor groups. This highly-desirable, non-classical behaviour signals the quantum nature of transport through such wires. It arises, because with increasing length, the tendency for electrical conductance to decay is compensated by a decrease in their HOMO-LUMO gap. Our study reveals the potential of these molecular wires as interconnects in future molecular-scale circuitry.

If the factors controlling the decay in single-molecule electrical conductance G with molecular length L could be understood and controlled, then this would be a significant step forward in the design of high-conductance molecular wires. For a wide variety of molecules conducting by phase coherent tunneling, conductance G decays with length following the relationship G = Aexp-\b{\eta}L. It is widely accepted that the attenuation coefficient \b{\eta} is determined by the position of the Fermi energy of the electrodes relative to the energy of frontier orbitals of the molecular bridge, whereas the terminal anchor groups which bind to the molecule to the electrodes contribute to the pre-exponential factor A. We examine this premise for several series of molecules which contain a central conjugated moiety (phenyl, viologen or {\alpha}-terthiophene) connected on either side to alkane chains of varying length, with each end terminated by thiol or thiomethyl anchor groups. In contrast with this expectation, we demonstrate both experimentally and theoretically that additional electronic states located on thiol anchor groups can significantly decrease the value of \b{eta}, by giving rise to resonances close to EF through coupling to the bridge moiety. This interplay between the gateway states and their coupling to a central conjugated moiety in the molecular bridges creates a new design strategy for realising higher-transmission molecular wires by taking advantage of the electrode-molecule interface properties.

The thermoelectric figures of merit of pristine two-dimensional materials are predicted to be significantly less than unity, making them uncompetitive as thermoelectric materials. Here we elucidate a new strategy that overcomes this limitation by creating multi-layer nanoribbons of two different materials and allowing thermal and electrical currents to flow perpendicular to their planes. To demonstrate this enhancement of thermoelectric efficiency ZT, we analyse the thermoelectric performance of monolayer molybdenum disulphide (MoS2) sandwiched between two graphene monolayers and demonstrate that the cross-plane (CP) ZT is significantly enhanced compared with the pristine parent materials. For the parent monolayer of MoS2, we find that ZT can be as high as approximately 0.3, whereas monolayer graphene has a negligibly small ZT. In contrast for the graphene/MoS2/graphene heterostructure, we find that the CP ZT can be as large as 2.8. One contribution to this enhancement is a reduction of the thermal conductance of the van der Waals heterostructure compared with the parent materials, caused by a combination of boundary scattering at the MoS2/graphene interface which suppresses the phonons transmission and the lower Debye frequency of monolayer MoS2, which filters phonons from the monolayer graphene. A second contribution is an increase in the electrical conductance and Seebeck coefficient associated with molybdenum atoms at the edges of the nanoribbons.

We report quantum interference effects in the electrical conductance of chemical vapor deposited graphene nanoconstrictions fabricated using feedback controlled electroburning. The observed multimode Fabry-Perot interferences can be attributed to reflections at potential steps inside the channel. Sharp antiresonance features with a Fano line shape are observed. Theoretical modeling reveals that these Fano resonances are due to localized states inside the constriction, which couple to the delocalized states that also give rise to the Fabry-Perot interference patterns. This study provides new insight into the interplay between two fundamental forms of quantum interference in graphene nanoconstrictions.

Understanding the electronic and phononic transport properties of junctions consisting of a scattering region such as a nanoscale matters or molecules connected to two or more electrodes is the central basis for future nano and molecular scale applications. The theoretical and mathematical techniques to treat electron and phonon transport are leading to model the physical properties of nano and molecular scale junctions. My aim in this paper is to review the theoretical and mathematical techniques to treat electron and phonon transport in nano and molecular scale junctions leading to models of their physical properties. This helps not only to understand the experimental observations but also provides a vital design tool to develop strategies for molecular electronic building blocks, thermoelectric device and sensors.

If design principles for controlling quantum interference in single molecules could be elucidated and verified, then this will lay the foundations for exploiting such effects in nanoscale devices and thin-film materials.When the core of a graphene-like polyaromatic hydrocarbon (PAH) is weakly coupled to external electrodes by atoms i and j, the single-molecule electrical conductance sigma-ij depends on the choice of connecting atoms i,j. Furthermore, conductance ratios sigma-ij/sigma-lm corresponding to different connectivities i,j and l,m are determined by quantum interference within the PAH core. In this paper, we examine how such conductance ratios change when one of the carbon atoms within the "parent" PAH core is replaced by a heteroatom to yield a "daughter" molecule. For bipartite parental cores, in which odd-numbered sites are connected to even-numbered sites only, the effect of heteroatom substitution onto an odd-numbered site is summarized by the following qualitative rules: (a) When i and j are odd, both parent and daughter have low conductances (b) When i is odd and j is even, or vice versa both parent and daughter have high conductances (c) When i,j are both even, the parent has a low conductance and the daughter a high conductance. These rules are verified by comparison with density-functional calculations on naphthalene, anthracene, pyrene and anthanthrene cores connected via two different anchor groups to gold electrodes.

We investigate the molecular sensing properties of carbon nanotube-boron nitride-carbon nanotube (CNT-BN-CNT) junctions. We demonstrate that the electrical conductance of such a junction changes in response to the binding of an analyte molecule to the region of BN. The change in conductance depends on the length of the BN spacer and the position of the analyte and therefore we propose a method of statistically analysing conductance data. We demonstrate the ability to discriminate between analytes, by computing the conductance changes due to three analytes (benzene, thiol-capped oligoyne and a pyridyl-capped oligoyne) binding to junctions with five different lengths of BN spacer.

A robust nanoelectromechanical switch is proposed based upon an asymmetric pendant moiety anchored to an organic backbone between two C60 fullerenes, which in turn are connected to gold electrodes. Ab initio density functional calculations are used to demonstrate that an electric field induces rotation of the pendant group, leading to a non-linear current-voltage relation. The non-linearity is strong enough to lead to negative differential resistance at modest source-drain voltages.

Provided the electrical properties of electro-burnt graphene junctions can be understood and controlled, they have the potential to underpin the development of a wide range of future sub-10nm electrical devices. We examine both theoretically and experimentally the electrical conductance of electro-burnt graphene junctions at the last stages of nanogap formation. We account for the appearance of a counterintuitive increase in electrical conductance just before the gap forms. This is a manifestation of room-temperature quantum interference and arises from a combination of the semi-metallic band structure of graphene and a crossover from electrodes with multiple-path connectivity to single-path connectivity just prior to breaking. Therefore our results suggest that conductance enlargement prior to junction rupture is a signal of the formation of electro-burnt junctions, with a pico-scale current path formed from a single sp2-bond.

Understanding phonon transport at a molecular scale is fundamental to the development of high-performance thermoelectric materials for the conversion of waste heat into electricity. We have studied phonon and electron transport in alkane and oligoyne chains of various lengths and find that due to the more rigid nature of the latter, the phonon thermal conductances of oligoynes are counter intuitively lower than that of the corresponding alkanes. The thermal conductance of oligoynes decreases monotonically with increasing length, whereas the thermal conductance of alkanes initially increases with length and then decreases. This difference in behaviour arises from phonon filtering by the gold electrodes and disappears when higher-Debye-frequency electrodes are used. Consequently a molecule that better transmits higher-frequency phonon modes, combined with a low-Debye-frequency electrode that filters high-energy phonons is a viable strategy for suppressing phonon transmission through the molecular junctions. The low thermal conductance of oligoynes, combined with their higher thermopower and higher electrical conductance lead to yield a maximum thermoelectric figure of merit of ZT = 1.4, which is several orders of magnitude higher than for alkanes.

We examine the effect of a hexagonal boron nitride (hBN) substrate on electron transport through graphene nanojunctions just before gap formation. Junctions in vacuum and on hBN are formed using classical molecular dynamics to create initial structures, followed by relaxation using density functional theory. We find that the hBN only slightly reduces the current through the junctions at low biases. Furthermore due to quantum interference at the last moments of breaking, the current though a single carbon filament spanning the gap is found to be higher than the current through two filaments spanning the gap in parallel. This feature is present both in the presence of absence of hBN.

Experiments using a mechanically-controlled break junction and calculations based on density functional theory demonstrate a new magic ratio rule (MRR),which captures the contribution of connectivity to the electrical conductance of graphene-like aromatic molecules. When one electrode is connected to a site i and the other is connected to a site i' of a particular molecule, we assign the molecule a magic integer Mii'. Two molecules with the same aromatic core, but different pairs of electrode connection sites (i,i' and j,j' respectively) possess different magic integers Mii' and Mjj'. Based on connectivity alone, we predict that when the coupling to electrodes is weak and the Fermi energy of the electrodes lies close to the centre of the HOMO-LUMO gap, the ratio of their conductances is equal to (Mii' /Mjj')2. The MRR is exact for a tight binding representation of a molecule and a qualitative guide for real molecules.

If quantum interference patterns in the hearts of polycyclic aromatic hydrocarbons (PAHs) could be isolated and manipulated, then a significant step towards realizing the potential of single-molecule electronics would be achieved. Here we demonstrate experimentally and theoretically that a simple, parameter-free, analytic theory of interference patterns evaluated at the mid-point of the HOMO-LUMO gap (referred to as M-functions) correctly predicts conductance ratios of molecules with pyrene, naphthalene, anthracene, anthanthrene or azulene hearts. M-functions provide new design strategies for identifying molecules with phase-coherent logic functions and enhancing the sensitivity of molecular-scale interferometers., Comment: in J. Am. Chem. Soc. (2015)

A quantum circuit rule for combining quantum interference (QI) effects in the conductive properties of oligo(phenyleneethynylene) (OPE)-type molecules possessing three aromatic rings was investigated both experimentally and theoretically. Molecules were of the type X-Y-X, where X represents pyridyl anchors with para (p), meta (m) or ortho (o) connectivities and Y represents a phenyl ring with p and m connectivities. The conductances GXmX (GXpX) of molecules of the form X-m-X (X-p-X), with meta (para) connections in the central ring were predominantly lower (higher), irrespective of the meta, para, or ortho nature of the anchor groups X, demonstrating that conductance is dominated by the nature of QI in the central ring Y. The single-molecule conductances were found to satisfy the quantum circuit rule Gppp/Gpmp = Gmpm/Gmmm. This demonstrates that the contribution to the conductance from the central ring is independent of the para versus meta nature of the anchor groups.

Self-heating is a severe problem for high-power microelectronic devices. Graphene and few-layer graphene have attracted tremendous attention for heat removal thanks to their extraordinarily high in-plane thermal conductivity. However, this high thermal conductivity undergoes severe degradations caused by the contact with the substrate and the functionalization-induced point defects. Here we show that thermal management of a micro heater can be substantially improved via introduction of alternative heat-escaping channels implemented with graphene-based film covalently bonded to functionalized graphene oxide through silane molecules. Theoretical and experimental results demonstrate a counter-intuitive enhancement of the thermal conductivity of such a graphene-based film. This increase in the in-plane thermal conductivity of supported graphene is accompanied by an improvement on the graphene-substrates thermal contact. Using infrared thermal imaging, we demonstrate that the temperature of the hotspots can be lowered by 12 $^o$C in transistors operating at 130 W mm$^{-2}$ , which corresponds to half of an order-of-magnitude increase in the device lifetime. Ab initio and molecular dynamics simulations reveal that the functionalization constrains the cross-plane scattering of low frequency phonons, which in turn enhances in-plane heat conduction of the bonded graphene film by recovering the long flexural phonon lifetime.

We demonstrate the potential of perylene bisimide (PBI) for label-free sensing of organic molecules by investigating the change in electronic properties of five symmetric and asymmetric PBI derivatives, which share a common backbone, but are functionalised with various bay-area substituents. Density functional theory was combined with a Greens function scattering approach to compute the electrical conductance of each molecule attached to two gold electrodes by pyridyl anchor groups. We studied the change in their conductance in response to the binding of three analytes, namely TNT, BEDT-TTF and TCNE, and found that the five different responses provided a unique fingerprint for the discriminating sensing of each analyte. This ability to sense and discriminate was a direct consequence of the extended {\pi} system of the PBI backbone, which strongly binds the analytes, combined with the different charge distribution of the five PBI derivatives, which leads to a unique electrical response to analyte binding., Comment: J. Mater. Chem. C, 2015

The analytical electrical transport model of the Silicene, a single layer of sp3 bonded silicon atoms in the honeycomb lattice structure as a channel in the field effect transistor configuration is presented in this paper. Although the carrier concentration of the Silicene shows similar behavior to Graphene, there are some differences in the conductance behavior. Presented model shows increment in the total carrier and the conductance with the gate voltage as expected for conventional semiconductors which affected by the temperature only in the neutrality point. The minimum conductance is increased by the temperature whereas it remains stable in the degenerate regime. Presented analytical model is in good agreement with the numerical conductance calculation based on the implementation of the non-equilibrium Greens function method coupled to the density functional theory.

We propose a DNA sequencing scheme based on silicene nanopores. Using first principles theory, we compute the electrical properties of such pores in the absence and presence of nucleobases. Within a two-terminal geometry, we analyze the current-voltage relation in the presence of nucleobases with various orientations. We demonstrate that when nucleobases pass through a pore, even after sampling over many orientations, changes in the electrical properties of the ribbon can be used to discriminate between bases.