A scanning tunnelling microscope has been used to determine the conductance of single molecular w... more A scanning tunnelling microscope has been used to determine the conductance of single molecular wires with the configuration X-bridge-X, X-bridge-Y and Y-bridge-Y (X = thiol terminus and Y = COOH). We find that for molecular wires with mixed functional groups (X-bridge-Y) the single molecule conductance decreases with respect to the comparable symmetric molecules. These differences are confirmed by theoretical computations based on a combination of density functional theory and the non-equilibrium Green's functions formalism. This study demonstrates that the apparent contact resistance, as well as being highly sensitive to the type of the anchoring group, is also strongly influenced by contact-asymmetry of the single molecular junction which in this case decreases the transmission. This highlights that contact-asymmetry is a significant factor to be considered when evaluating nanoelectrical junctions incorporating single molecules.
We analyze the interplay between disorder and band structure in current perpendicular to the plan... more We analyze the interplay between disorder and band structure in current perpendicular to the planes (CPP) giant magnetoresistance (GMR). We consider finite magnetic multilayers attached to pure crystalline leads, described by a tight-binding simple cubic two-band model (s-d). Several models of disorder are considered, including random on-site potentials, lattice distortions, impurities, vacancies, and cross-section fluctuations. Magneto-transport properties are calculated in the zero-temperature zero-bias limit, within the Landauer-Buttiker formalism. Using a very efficient numerical scattering technique, we are able to perform simulations, over large length scales, and to investigate spin-transport in the ballistic, diffusive and localized regimes, as well as the crossover between them. The competition between disorder-induced mean free path reduction and disorder-induced spin asymmetry enhancement of the conductance highlights several different regimes of GMR.
We demonstrate a new technique for creating unique forms of pure sp2-bonded carbon and unpreceden... more We demonstrate a new technique for creating unique forms of pure sp2-bonded carbon and unprecedented hetero-molecules. These new structures, which we refer to as sculpturenes, are formed by sculpting selected shapes from bilayer graphene, hetero-bilayers or multi-layered materials and allowing the shapes to spontaneously reconstruct. The simplest sculpturene is topologically equivalent to a torus, with dimensions comparable to those of fullerenes. The topology of these new molecular structures is stable against atomic scale defects.
Understanding phonon transport at a molecular scale is fundamental to the development of high-per... more 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 t...
We studied charge transport phenomena through a core substituted naphthalenediimide (NDI) single-... more We studied charge transport phenomena through a core substituted naphthalenediimide (NDI) single-molecule junctions using the electrochemical STM-based break junction technique in combination with DFT calculations. The conductance switch among three well-defined states is acquired by electrochemically controlling the redox state of the pendent diimide unit of the molecule in ionic liquid, and the conductance difference is more than one order of magnitude between di-anion states and neutral state. The potential dependent charge transport characteristics of the NDI molecules are confirmed by DFT calculations accounting for electrochemical double-layer effects on the conductance of the NDI junctions. This work suggests that the integration of redox unit in the pendent position with strong coupling to molecular backbone can significantly tune the charge transport of the single-molecule device by controlling different redox states.
A quantum circuit rule for combining quantum interference (QI) effects in the conductive properti... more 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.
We study the effect on CPP GMR of changing the order of the layers in a multilayer. Using a tight... more We study the effect on CPP GMR of changing the order of the layers in a multilayer. Using a tight-binding simple cubic two band model (s-d), magneto-transport properties are calculated in the zero-temperature, zero-bias limit, within the Landauer-Buttiker formalism. We demonstrate that for layers of different thicknesses formed from a single magnetic metal and multilayers formed from two magnetic metals, the GMR ratio and its dependence on disorder is sensitive to the order of the layers. This effect disappears in the limit of large disorder, where the results of the widely-used Boltzmann approach to transport are restored.
We present a study of the thermopower S and the dimensionless figure of merit ZT in molecules san... more We present a study of the thermopower S and the dimensionless figure of merit ZT in molecules sandwiched between gold electrodes. We show that for molecules with side groups, the shape of the transmission coefficient can be dramatically modified by Fano resonances near the Fermi energy, which can be tuned to produce huge increases in S and ZT. This shows that molecules exhibiting Fano resonances have a high efficiency of thermoelectric cooling which is not present for conventional un-gated molecules with only delocalized states along their backbone.
Using a first principles approach to electron transport, we calculate the electrical and thermoel... more Using a first principles approach to electron transport, we calculate the electrical and thermoelectrical transport properties of a series of molecular wires containing benzo-difuran subunits. We demonstrate that the side groups introduce Fano resonances, the energy of which is changing with the electronegativity of selected atoms in it. We also study the relative effect of single, double or triple bonds along the molecular backbone and find that single bonds yield the highest thermopower, approximately 22μV/K at room temperature, which is comparable with the highest measured values for single-molecule thermopower reported to date.
Devices formed from single molecules attached to noble-metal electrodes exhibit large conductance... more Devices formed from single molecules attached to noble-metal electrodes exhibit large conductance fluctuations, which inhibit their development as reproducible functional units. We demonstrate that single molecules with planar anchor groups attached to carbon-based electrodes are more resilient to atomic-scale variation in the contacts and exhibit significantly lower conductance fluctuations. We examine the conductance of a 2,6-dibenzylamino core-substituted naphthalenediimide chromophore attached to carbon electrodes by either phenanthrene anchors or more extended anchor groups, which include oligophenylene ethynylene spacers. We demonstrate that for the more spatially extended anchor groups conductance fluctuations are significantly reduced. The current-voltage characteristic arising from long-range tunneling is found to be strongly nonlinear with pronounced conductance suppression below a threshold voltage of approximately 2.5 V.
An effective random matrix theory description is developed for the universal gap fluctuations and... more An effective random matrix theory description is developed for the universal gap fluctuations and the ensemble averaged density of states of chaotic Andreev billiards for finite Ehrenfest time. It yields a very good agreement with the numerical calculation for Sinai-Andreev billiards. A systematic linear decrease of the mean field gap with increasing Ehrenfest time Ï„_E is observed but its derivative with respect to Ï„_E is in between two competing theoretical predictions and close to that of the recent numerical calculations for Andreev map. The exponential tail of the density of states is interpreted semi-classically.
We demonstrate the potential of perylene bisimide (PBI) for label-free sensing of organic molecul... more 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 π 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 t...
If design principles for controlling quantum interference in single molecules could be elucidated... more 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 follow...
Within the microscopic Bogoliubov--de Gennes (BdG) formalism an exact quantization condition for ... more Within the microscopic Bogoliubov--de Gennes (BdG) formalism an exact quantization condition for Andreev bound states of the ferromagnetic-superconducting hybrid systems of box geometry is derived and a semi-classical formula for the density of states is obtained. The semi-classical formula is shown to agree with the exact result, even when the exchange field h, is much larger than the superconductor order parameter, provided h is small compared with the Fermi energy.
Self-heating is a severe problem for high-power microelectronic devices. Graphene and few-layer g... more 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...
Results are presented for the electron current in gold chiral nanotubes (AuNTs). Starting from th... more Results are presented for the electron current in gold chiral nanotubes (AuNTs). Starting from the band structure of (4,3) and (5,3) AuNTs, we find that the magnitude of the chiral currents are greater than those found in carbon nanotubes. We also calculate the associated magnetic flux inside the tubes and find this to be higher than the case of carbon nanotubes. Although (4,3) and (5,3) AuNTs carry transverse momenta of similar magnitudes, the low-bias magnetic flux carried by the former is far greater than that carried by the latter. This arises because the low-bias longitudinal current carried by a (4,3) AuNT is significantly smaller than that of a (5,3) AuNT.
We examine the effect of a hexagonal boron nitride (hBN) substrate on electron transport through ... more 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.
When a molecule is bound to external electrodes by terminal anchor groups, the latter are of para... more When a molecule is bound to external electrodes by terminal anchor groups, the latter are of paramount importance in determining the electrical conductance of the resulting molecular junction. Here we...
A scanning tunnelling microscope has been used to determine the conductance of single molecular w... more A scanning tunnelling microscope has been used to determine the conductance of single molecular wires with the configuration X-bridge-X, X-bridge-Y and Y-bridge-Y (X = thiol terminus and Y = COOH). We find that for molecular wires with mixed functional groups (X-bridge-Y) the single molecule conductance decreases with respect to the comparable symmetric molecules. These differences are confirmed by theoretical computations based on a combination of density functional theory and the non-equilibrium Green's functions formalism. This study demonstrates that the apparent contact resistance, as well as being highly sensitive to the type of the anchoring group, is also strongly influenced by contact-asymmetry of the single molecular junction which in this case decreases the transmission. This highlights that contact-asymmetry is a significant factor to be considered when evaluating nanoelectrical junctions incorporating single molecules.
We analyze the interplay between disorder and band structure in current perpendicular to the plan... more We analyze the interplay between disorder and band structure in current perpendicular to the planes (CPP) giant magnetoresistance (GMR). We consider finite magnetic multilayers attached to pure crystalline leads, described by a tight-binding simple cubic two-band model (s-d). Several models of disorder are considered, including random on-site potentials, lattice distortions, impurities, vacancies, and cross-section fluctuations. Magneto-transport properties are calculated in the zero-temperature zero-bias limit, within the Landauer-Buttiker formalism. Using a very efficient numerical scattering technique, we are able to perform simulations, over large length scales, and to investigate spin-transport in the ballistic, diffusive and localized regimes, as well as the crossover between them. The competition between disorder-induced mean free path reduction and disorder-induced spin asymmetry enhancement of the conductance highlights several different regimes of GMR.
We demonstrate a new technique for creating unique forms of pure sp2-bonded carbon and unpreceden... more We demonstrate a new technique for creating unique forms of pure sp2-bonded carbon and unprecedented hetero-molecules. These new structures, which we refer to as sculpturenes, are formed by sculpting selected shapes from bilayer graphene, hetero-bilayers or multi-layered materials and allowing the shapes to spontaneously reconstruct. The simplest sculpturene is topologically equivalent to a torus, with dimensions comparable to those of fullerenes. The topology of these new molecular structures is stable against atomic scale defects.
Understanding phonon transport at a molecular scale is fundamental to the development of high-per... more 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 t...
We studied charge transport phenomena through a core substituted naphthalenediimide (NDI) single-... more We studied charge transport phenomena through a core substituted naphthalenediimide (NDI) single-molecule junctions using the electrochemical STM-based break junction technique in combination with DFT calculations. The conductance switch among three well-defined states is acquired by electrochemically controlling the redox state of the pendent diimide unit of the molecule in ionic liquid, and the conductance difference is more than one order of magnitude between di-anion states and neutral state. The potential dependent charge transport characteristics of the NDI molecules are confirmed by DFT calculations accounting for electrochemical double-layer effects on the conductance of the NDI junctions. This work suggests that the integration of redox unit in the pendent position with strong coupling to molecular backbone can significantly tune the charge transport of the single-molecule device by controlling different redox states.
A quantum circuit rule for combining quantum interference (QI) effects in the conductive properti... more 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.
We study the effect on CPP GMR of changing the order of the layers in a multilayer. Using a tight... more We study the effect on CPP GMR of changing the order of the layers in a multilayer. Using a tight-binding simple cubic two band model (s-d), magneto-transport properties are calculated in the zero-temperature, zero-bias limit, within the Landauer-Buttiker formalism. We demonstrate that for layers of different thicknesses formed from a single magnetic metal and multilayers formed from two magnetic metals, the GMR ratio and its dependence on disorder is sensitive to the order of the layers. This effect disappears in the limit of large disorder, where the results of the widely-used Boltzmann approach to transport are restored.
We present a study of the thermopower S and the dimensionless figure of merit ZT in molecules san... more We present a study of the thermopower S and the dimensionless figure of merit ZT in molecules sandwiched between gold electrodes. We show that for molecules with side groups, the shape of the transmission coefficient can be dramatically modified by Fano resonances near the Fermi energy, which can be tuned to produce huge increases in S and ZT. This shows that molecules exhibiting Fano resonances have a high efficiency of thermoelectric cooling which is not present for conventional un-gated molecules with only delocalized states along their backbone.
Using a first principles approach to electron transport, we calculate the electrical and thermoel... more Using a first principles approach to electron transport, we calculate the electrical and thermoelectrical transport properties of a series of molecular wires containing benzo-difuran subunits. We demonstrate that the side groups introduce Fano resonances, the energy of which is changing with the electronegativity of selected atoms in it. We also study the relative effect of single, double or triple bonds along the molecular backbone and find that single bonds yield the highest thermopower, approximately 22μV/K at room temperature, which is comparable with the highest measured values for single-molecule thermopower reported to date.
Devices formed from single molecules attached to noble-metal electrodes exhibit large conductance... more Devices formed from single molecules attached to noble-metal electrodes exhibit large conductance fluctuations, which inhibit their development as reproducible functional units. We demonstrate that single molecules with planar anchor groups attached to carbon-based electrodes are more resilient to atomic-scale variation in the contacts and exhibit significantly lower conductance fluctuations. We examine the conductance of a 2,6-dibenzylamino core-substituted naphthalenediimide chromophore attached to carbon electrodes by either phenanthrene anchors or more extended anchor groups, which include oligophenylene ethynylene spacers. We demonstrate that for the more spatially extended anchor groups conductance fluctuations are significantly reduced. The current-voltage characteristic arising from long-range tunneling is found to be strongly nonlinear with pronounced conductance suppression below a threshold voltage of approximately 2.5 V.
An effective random matrix theory description is developed for the universal gap fluctuations and... more An effective random matrix theory description is developed for the universal gap fluctuations and the ensemble averaged density of states of chaotic Andreev billiards for finite Ehrenfest time. It yields a very good agreement with the numerical calculation for Sinai-Andreev billiards. A systematic linear decrease of the mean field gap with increasing Ehrenfest time Ï„_E is observed but its derivative with respect to Ï„_E is in between two competing theoretical predictions and close to that of the recent numerical calculations for Andreev map. The exponential tail of the density of states is interpreted semi-classically.
We demonstrate the potential of perylene bisimide (PBI) for label-free sensing of organic molecul... more 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 π 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 t...
If design principles for controlling quantum interference in single molecules could be elucidated... more 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 follow...
Within the microscopic Bogoliubov--de Gennes (BdG) formalism an exact quantization condition for ... more Within the microscopic Bogoliubov--de Gennes (BdG) formalism an exact quantization condition for Andreev bound states of the ferromagnetic-superconducting hybrid systems of box geometry is derived and a semi-classical formula for the density of states is obtained. The semi-classical formula is shown to agree with the exact result, even when the exchange field h, is much larger than the superconductor order parameter, provided h is small compared with the Fermi energy.
Self-heating is a severe problem for high-power microelectronic devices. Graphene and few-layer g... more 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...
Results are presented for the electron current in gold chiral nanotubes (AuNTs). Starting from th... more Results are presented for the electron current in gold chiral nanotubes (AuNTs). Starting from the band structure of (4,3) and (5,3) AuNTs, we find that the magnitude of the chiral currents are greater than those found in carbon nanotubes. We also calculate the associated magnetic flux inside the tubes and find this to be higher than the case of carbon nanotubes. Although (4,3) and (5,3) AuNTs carry transverse momenta of similar magnitudes, the low-bias magnetic flux carried by the former is far greater than that carried by the latter. This arises because the low-bias longitudinal current carried by a (4,3) AuNT is significantly smaller than that of a (5,3) AuNT.
We examine the effect of a hexagonal boron nitride (hBN) substrate on electron transport through ... more 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.
When a molecule is bound to external electrodes by terminal anchor groups, the latter are of para... more When a molecule is bound to external electrodes by terminal anchor groups, the latter are of paramount importance in determining the electrical conductance of the resulting molecular junction. Here we...
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Papers by Colin Lambert