RESUMEN
Break-junction techniques provide the possibility to study electric and thermoelectric properties of single-molecule junctions in great detail. These techniques rely on the same principle of controllably breaking metallic contacts in order to create single-molecule junctions, whilst keeping track of the junction's conductance. Here, we compare results from mechanically controllable break junction (MCBJ) and scanning tunneling microscope (STM) methods, while characterizing conductance properties of the same novel mechanosensitive para- and meta-connected naphtalenophane compounds. In addition, thermopower measurements are carried out for both compounds using the STM break junction (STM-BJ) technique. For the conductance experiments, the same data processing using a clustering analysis is performed. We obtain to a large extent similar results for both methods, although values of conductance and stretching lengths for the STM-BJ technique are slightly larger in comparison with the MCBJ. STM-BJ thermopower experiments show similar Seebeck coefficients for both compounds. An increase in the Seebeck coefficient is revealed, whilst the conductance decreases, after which it saturates at around 10 µV K-1. This phenomenon is studied theoretically using a tight binding model. It shows that changes of molecule-electrode electronic couplings combined with shifts of the resonance energies explain the correlated behavior of conductance and Seebeck coefficient.
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Thermoelectric materials have garnered significant interest for their potential to efficiently convert waste heat into electrical energy at room temperature without moving parts or harmful emissions. This study investigated the impact of the HOMO-LUMO (H-L) gap on the thermoelectric properties of three distinct classes of organic compounds: conjugated aromatics (isoindigos (IIGs)), quinoidal molecules (benzodipyrrolidones (BDPs)), and donor-acceptor systems (bis(pyrrol-2-yl)squaraines (BPSs)). These compounds were chosen for their structural simplicity and linear π-conjugated conductance paths, which promote high electrical conductance and minimize complications from quantum interference. Single-molecule thermoelectric measurements revealed that despite their low H-L gaps, the Seebeck coefficients of these compounds remain low. The alignment of the frontier orbitals relative to the Fermi energy was found to play a crucial role in determining the Seebeck coefficients, as exemplified by the BDP compounds. Theoretical calculations support these findings and suggest that anchor group selection could further enhance the thermoelectric behavior of these types of molecules.
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We report a combined experimental and theoretical study of a series of thiomethyl (SMe) anchored cross-conjugated molecules featuring an acyclic central bridging ketone and their analogous skipped-conjugated alcohol derivatives. Studies of these molecules in a gold|single-molecule|gold junction using scanning tunneling microscopy-break junction techniques reveal a similar conductance (G) value for both the cross-conjugated molecules and their skipped-conjugated partners. Theoretical studies based on density functional theory of the molecules in their optimum geometries in the junction reveal the reason for this similarity in conductance, as the predicted conductance for the alcohol series of compounds varies more with the tilt angle. Thermopower measurements reveal a higher Seebeck coefficient (S) for the cross-conjugated ketone molecules relative to the alcohol derivatives, with a particularly high S for the biphenyl derivative 3a (-15.6 µV/K), an increase of threefold compared to its alcohol analog. The predicted behavior of the quantum interference (QI) in this series of cross-conjugated molecules is found to be constructive, though the appearance of a destructive QI feature for 3a is due to the degeneracy of the HOMO orbital and may explain the enhancement of the value of S for this molecule.
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The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.
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Near-field radiative heat transfer (NFRHT) between planar metallic surfaces was computationally explored over five decades ago by Polder and van Hove [Phys. Rev. B 4, 3303 (1971)PLRBAQ0556-280510.1103/PhysRevB.4.3303]. These studies predicted that, as the gap size (d) between the surfaces decreased, the radiative heat flux first increases by several orders of magnitude until d is â¼100 nm after which the heat flux saturates. However, despite both the fundamental and practical importance of these predictions, the combined enhancement and saturation of NFRHT at small gaps in metallic surfaces remains experimentally unverified. Here, we probe NFRHT between planar metallic (Pt, Au) surfaces and show that RHT rates can exceed the far-field rate by over a thousand times when d is reduced to â¼25 nm. More importantly, we show that for small values of d RHT saturates due to the dominant contributions from transverse electric evanescent modes. Our results are in excellent agreement with the predictions of fluctuational electrodynamics and are expected to inform the development of technologies such as near-field thermophotovoltaics, radiative heat-assisted magnetic recording, and nanolithography.
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Controlling charge transport through molecules is challenging because it requires engineering of the energy of molecular orbitals involved in the transport process. While side groups are central to maintaining solubility in many molecular materials, their role in modulating charge transport through single-molecule junctions has received less attention. Here, using two break-junction techniques and computational modeling, we investigate systematically the effect of electron-donating and -withdrawing side groups on the charge transport through single molecules. By characterizing the conductance and thermopower, we demonstrate that side groups can be used to manipulate energy levels of the transport orbitals. Furthermore, we develop a novel statistical approach to model quantum transport through molecular junctions. The proposed method does not treat the electrodes' chemical potential as a free parameter and leads to more robust prediction of electrical conductance as confirmed by our experiment. The new method is generic and can be used to predict the conductance of molecules.
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This paper describes the syntheses of several functionalized dihydropyrene (DHP) molecular switches with different substitution patterns. Regioselective nucleophilic alkylation of a 5-substituted dimethyl isophthalate allowed the development of a workable synthetic protocol for the preparation of 2,7-alkyne-functionalized DHPs. Synthesis of DHPs with surface-anchoring groups in the 2,7- and 4,9-positions is described. The molecular structures of several intermediates and DHPs were elucidated by X-ray single-crystal diffraction. Molecular properties and switching capabilities of both types of DHPs were assessed by light irradiation experiments, spectroelectrochemistry, and cyclic voltammetry. Spectroelectrochemistry, in combination with density functional theory (DFT) calculations, shows reversible electrochemical switching from the DHP forms to the cyclophanediene (CPD) forms. Charge-transport behavior was assessed in single-molecule scanning tunneling microscope (STM) break junctions, combined with density functional theory-based quantum transport calculations. All DHPs with surface-contacting groups form stable molecular junctions. Experiments show that the molecular conductance depends on the substitution pattern of the DHP motif. The conductance was found to decrease with increasing applied bias.
RESUMEN
For the purpose of creating single-molecule junctions, which can convert a temperature difference ΔT into a voltage ΔV via the Seebeck effect, it is of interest to screen molecules for their potential to deliver high values of the Seebeck coefficient S = -ΔV/ΔT. Here we demonstrate that insight into molecular-scale thermoelectricity can be obtained by examining the widths and extreme values of Seebeck histograms. Using a combination of experimental scanning-tunnelling-microscopy-based transport measurements and density-functional-theory-based transport calculations, we study the electrical conductance and Seebeck coefficient of three endohedral metallofullerenes (EMFs) Sc3N@C80, Sc3C2@C80, and Er3N@C80, which based on their structures, are selected to exhibit different degrees of charge inhomogeneity and geometrical disorder within a junction. We demonstrate that standard deviations in the Seebeck coefficient σS of EMF-based junctions are correlated with the geometric standard deviation σ and the charge inhomogeneity σq. We benchmark these molecules against C60 and demonstrate that both σq, σS are the largest for Sc3C2@C80, both are the smallest for C60 and for the other EMFs, they follow the order Sc3C2@C80 > Sc3N@C80 > Er3N@C80 > C60. A large value of σS is a sign that a molecule can exhibit a wide range of Seebeck coefficients, which means that if orientations corresponding to high values can be selected and controlled, then the molecule has the potential to exhibit high-performance thermoelectricity. For the EMFs studied here, large values of σS are associated with distributions of Seebeck coefficients containing both positive and negative signs, which reveals that all these EMFs are bi-thermoelectric materials.
RESUMEN
Organic thermoelectric materials have potential for wearable heating, cooling, and energy generation devices at room temperature. For this to be technologically viable, high-conductance (G) and high-Seebeck-coefficient (S) materials are needed. For most semiconductors, the increase in S is accompanied by a decrease in G. Here, using a combined experimental and theoretical investigation, we demonstrate that a simultaneous enhancement of S and G can be achieved in single organic radical molecules, thanks to their intrinsic spin state. A counterintuitive quantum interference (QI) effect is also observed in stable Blatter radical molecules, where constructive QI occurs for a meta-connected radical, leading to further enhancement of thermoelectric properties. Compared to an analogous closed-shell molecule, the power factor is enhanced by more than 1 order of magnitude in radicals. These results open a new avenue for the development of organic thermoelectric materials operating at room temperature.
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Molecules capable of mediating charge transport over several nanometers with minimal decay in conductance have fundamental and technological implications. Polymethine cyanine dyes are fascinating molecular wires because up to a critical length, they have no bond-length alternation (BLA) and their electronic structure resembles a one-dimensional free-electron gas. Beyond this threshold, they undergo a symmetry-breaking Peierls transition, which increases the HOMO-LUMO gap. We have investigated cationic cyanines with central polymethine chains of 5-13 carbon atoms (Cy3+-Cy11+). The absorption spectra and crystal structures show that symmetry breaking is sensitive to the polarity of the medium and the size of the counterion. X-ray crystallography reveals that Cy9·PF6 and Cy11·B(C6F5)4 are Peierls distorted, with high BLA at one end of the π-system, away from the partially delocalized positive charge. This pattern of BLA distribution resembles that of solitons in polyacetylene. The single-molecule conductance is essentially independent of molecular length for the polymethine salts of Cy3+-Cy11+ with the large B(C6F5)4- counterion, but with the PF6- counterion, the conductance decreases for the longer molecules, Cy7+-Cy11+, because this smaller anion polarizes the π-system, inducing a symmetry-breaking transition. At higher bias (0.9 V), the conductance of the shorter chains, Cy3+-Cy7+, increases with length (negative attenuation factor, ß = -1.6 nm-1), but the conductance still drops in Cy9+ and Cy11+ with the small polarizing PF6- counteranion.
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The most probable single-molecule conductance of each member of a series of 12 conjugated molecular wires, 6 of which contain either a ruthenium or platinum center centrally placed within the backbone, has been determined. The measurement of a small, positive Seebeck coefficient has established that transmission through these molecules takes place by tunneling through the tail of the HOMO resonance near the middle of the HOMO-LUMO gap in each case. Despite the general similarities in the molecular lengths and frontier-orbital compositions, experimental and computationally determined trends in molecular conductance values across this series cannot be satisfactorily explained in terms of commonly discussed "single-parameter" models of junction conductance. Rather, the trends in molecular conductance are better rationalized from consideration of the complete molecular junction, with conductance values well described by transport calculations carried out at the DFT level of theory, on the basis of the Landauer-Büttiker model.
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The ability to control the charge state of individual molecules wired in two-terminal single-molecule junctions is a key challenge in molecular electronics, particularly in relation to the development of molecular memory and other computational componentry. Here we demonstrate that single porphyrin molecular junctions can be reversibly charged and discharged at elevated biases under ambient conditions due to the presence of a localised molecular eigenstate close to the Fermi edge of the electrodes. In particular, we can observe long-lived charge-states with lifetimes upwards of 1-10 seconds after returning to low bias and large changes in conductance, in excess of 100-fold at low bias. Our theoretical analysis finds charge-state lifetimes within the same time range as the experiments. The ambient operation demonstrates that special conditions such as low temperatures or ultra-high vacuum are not essential to observe hysteresis and stable charged molecular junctions.
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The effects of antiaromaticity and destructive quantum interference (DQI) are investigated on the charge transport through dibenzo-[a,e]pentalene (DBP). 5,10-Connectivity gives high single-molecule conductance whereas 2,7 gives low conductance due to DQI. Comparison of the 5,10-DBP with phenyl and anthracene analogues yields the trend GDBP ≈ GAnth > GPh, despite the aromatic anthracene having a larger HOMO-LUMO gap than 5,10-DBP. This is explained by unfavourable level alignment for 5,10-DBP.
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The single-molecule conductance of a series of BN-acene-like derivatives has been measured by using scanning tunneling break-junction techniques. A strategic design of the target molecules has allowed us to include azaborine units in positions that unambiguously ensure electron transport through both heteroatoms, which is relevant for the development of customized BN-doped nanographenes. We show that the conductance of the anthracene azaborine derivative is comparable to that of the pristine all-carbon anthracene compound. Notably, this heteroatom substitution has also allowed us to perform similar measurements on the corresponding pentacene-like compound, which is found to have a similar conductance, thus evidencing that B-N doping could also be used to stabilize and characterize larger acenes for molecular electronics applications. Our conclusions are supported by state-of-the-art transport calculations.
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We report measurements on gold|single-molecule|gold junctions, using a modified scanning tunneling microscope-break junction (STM-BJ) technique, of the Seebeck coefficient and electrical conductance of a series of bridged biphenyl molecules, with meta connectivities to pyridyl anchor groups. These data are compared with a previously reported study of para-connected analogues. In agreement with a tight binding model, the electrical conductance of the meta series is relatively low and is sensitive to the nature of the bridging groups, whereas in the para case the conductance is higher and relatively insensitive to the presence of the bridging groups. This difference in sensitivity arises from the presence of destructive quantum interference in the π system of the unbridged aromatic core, which is alleviated to different degrees by the presence of bridging groups. More precisely, the Seebeck coefficient of meta-connected molecules was found to vary between -6.1 µV K-1 and -14.1 µV K-1, whereas that of the para-connected molecules varied from -5.5 µV K-1 and -9.0 µV K-1.
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We present microfabricated thermal actuators to engineer the biaxial strain in two-dimensional (2D) materials. These actuators are based on microheater circuits patterned onto the surface of a polymer with a high thermal expansion coefficient. By running current through the microheater one can vary the temperature of the polymer and induce a controlled biaxial expansion of its surface. This controlled biaxial expansion can be transduced to biaxial strain to 2D materials, placed onto the polymer surface, which in turn induces a shift of the optical spectrum. Our thermal strain actuators can reach a maximum biaxial strain of 0.64%, and they can be modulated at frequencies up to 8 Hz. The compact geometry of these actuators results in a negligible spatial drift of 0.03 µm/°C, which facilitates their integration in optical spectroscopy measurements. We illustrate the potential of this strain engineering platform to fabricate a strain-actuated optical modulator with single-layer MoS2.
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We studied the electron-transport properties of ten different amino acids and one dimer (di-methionine) using the mechanically controlled break-junction (MCBJ) technique. For methionine and cysteine, additional measurements were performed with the scanning tunneling microscope break-junction (STM-BJ) technique. By means of a statistical clustering technique, we identified several conductance groups for each of the molecules considered. Ab initio calculations revealed that the observed broad conductance distribution stems from the possibility of various binding geometries which can be formed during stretching combined with a multitude of possible conformational changes. The results suggest that it would be helpful to explore different experimental techniques such as recognition tunneling and conditions to help identify the nature of amino-acid-based junctions even further, for example, with the goal to establish a firm platform for their unambiguous recognition by tunneling break-junction experiments.
Asunto(s)
Aminoácidos/química , Técnicas Electroquímicas/métodos , Análisis por Conglomerados , Transporte de Electrón , Microscopía de Túnel de RastreoRESUMEN
Charge transport is strongly suppressed by destructive quantum interference (DQI) in meta-connected 1,1'-biphenyl-containing molecules, resulting in low electrical conductance. Surprisingly, we have found that DQI is almost entirely overcome by adding a bridging carbonyl, to yield a cross-conjugated fluorenone. This contrasts with other π-systems, such as para-connected anthraquinone, where cross-conjugation results in low conductance.
RESUMEN
Cumulenes are sometimes described as "metallic" because an infinitely long cumulene would have the band structure of a metal. Herein, we report the single-molecule conductance of a series of cumulenes and cumulene analogues, where the number of consecutive C=C bonds in the core is n=1, 2, 3, and 5. The [n]cumulenes with n=3 and 5 have almost the same conductance, and they are both more conductive than the alkene (n=1). This is remarkable because molecular conductance normally falls exponentially with length. The conductance of the allene (n=2) is much lower, because of its twisted geometry. Computational simulations predict a similar trend to the experimental results and indicate that the low conductance of the allene is a general feature of [n]cumulenes where n is even. The lack of length dependence in the conductance of [3] and [5]cumulenes is attributed to the strong decrease in the HOMO-LUMO gap with increasing length.