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Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements which can be used to determine the difference in configurational entropy between the redox states of a nanoscale system involved in conductance without any prior assumptions about its structure or microscopic dynamics.

2D Materials 8(1), 015031 (2021). doi:10.1088/2053-1583/abbecd, Published by IOP Publ., Bristol

Paper has the potential to dramatically reduce the cost of electronic components. In fact, paper is 10 000 times cheaper than crystalline silicon, motivating the research to integrate electronic materials on paper substrates. Among the different electronic materials, van der Waals materials are attracting the interest of the scientific community working on paper-based electronics because of the combination of high electrical performance and mechanical flexibility. Up to now, different methods have been developed to pattern conducting, semiconducting and insulating van der Waals materials on paper but the integration of superconductors remains elusive. Here, the deposition of NbSe2, an illustrative van der Waals superconductor, on standard copy paper is demonstrated. The deposited NbSe2 films on paper display superconducting properties (e.g. observation of Meissner effect and resistance drop to zero-resistance state when cooled down below its critical temperature) similar to those of bulk NbSe2., Paper has the potential to dramatically reduce the cost of electronic components but the integration of electronic materials is challenging. Here the integration of NbSe2, a van der Waals superconductor, on paper is demonstrated.

Paper holds the promise to replace silicon substrates in applications like internet of things or disposable electronics that require ultra-low-cost electronic components and an environmentally friendly electronic waste management. In the last years, spurred by the abovementioned properties of paper as a substrate and the exceptional electronic, mechanical and optical properties of van der Waals (vdW) materials, many research groups have worked towards the integration of vdW materials-based devices on paper. Recently, a method to deposit a continuous film of densely packed interconnects of vdW materials on paper by simply rubbing the vdW crystals against the rough surface of paper has been presented. This method utilizes the weak interlayer vdW interactions and allows cleaving of the crystals into micro platelets through the abrasion against the paper. Here, we aim to illustrate the general character and the potential of this technique by fabricating films of 39 different vdW materials (including superconductors, semi-metals, semiconductors, and insulators) on standard copier paper. We have thoroughly characterized their optical properties showing their high optical quality: one can easily resolve the absorption band edge of semiconducting vdW materials and even the excitonic features present in some vdW materials with high exciton binding energy. We also measured the electrical resistivity for several vdW materials films on paper finding exceptionally low values, which are in some cases, orders of magnitude lower than those reported for analogous films produced by inkjet printing. We finally demonstrate the fabrication of field-effect devices with vdW materials on paper using the paper substrate as an ionic gate., Comment: 4 figures in main text, 21 figures in Supp. Info

We report on charge transport across single short peptides using the Mechanically Controlled Break Junction (MCBJ) method. We record thousands of electron transport events across single-molecule junctions and with an unsupervised machine learning algorithm, we identify several classes of traces with multifarious conductance values that may correspond to different peptide conformations. Data analysis shows that very short peptides, which are more rigid, show conductance plateaus at low conductance values of about 10−3G0and below, withG0being the conductance quantum, whereas slightly longer, more flexible peptides also show plateaus at higher values. Fully stretched peptide chains exhibit conductance values that are of the same order as that of alkane chains of similar length. The measurements show that in the case of short peptides, different compositions and molecular lengths offer a wide range of junction conformations. Such information is crucial to understand mechanism(s) of charge transport in and across peptide-based biomolecules.

Paper based thermoresistive sensors are fabricated by rubbing WS2 powder against a piece of standard copier paper, like the way a pencil is used to write on paper. The abrasion between the layered material and the rough paper surface erodes the material, breaking the weak van der Waals interlayer bonds, yielding a film of interconnected platelets. The resistance of WS2 presents a strong temperature dependence, as expected for a semiconductor material in which charge transport is due to thermally activated carriers. This strong temperature dependence makes the paper supported WS2 devices extremely sensitive to small changes in temperature. This exquisite thermal sensitivity, and their fast response times to sudden temperature changes, is exploited thereby demonstrating the usability of a WS2-on-paper thermal sensor in a respiration monitoring device.

Ultrafast optical control of magnetic anisotropy in a van der Waals antiferromagnet activates a sub-THz two-dimensional magnon., Van der Waals magnets provide an ideal playground to explore the fundamentals of low-dimensional magnetism and open opportunities for ultrathin spin-processing devices. The Mermin-Wagner theorem dictates that as in reduced dimensions isotropic spin interactions cannot retain long-range correlations, the long-range spin order is stabilized by magnetic anisotropy. Here, using ultrashort pulses of light, we control magnetic anisotropy in the two-dimensional van der Waals antiferromagnet NiPS3. Tuning the photon energy in resonance with an orbital transition between crystal field split levels of the nickel ions, we demonstrate the selective activation of a subterahertz magnon mode with markedly two-dimensional behavior. The pump polarization control of the magnon amplitude confirms that the activation is governed by the photoinduced magnetic anisotropy axis emerging in response to photoexcitation of ground state electrons to states with a lower orbital symmetry. Our results establish pumping of orbital resonances as a promising route for manipulating magnetic order in low-dimensional (anti)ferromagnets.

Theoretical studies suggest that mastering the thermocurrent through single molecules can lead to thermoelectric energy harvesters with unprecedentedly high efficiencies.

We fabricate paper-supported semiconducting devices by rubbing a layered molybdenum disulfide (MoS

Graphene quantum dots (QDs) are intensively studied as platforms for the next generation of quantum electronic devices. Fine tuning of the transport properties in monolayer graphene QDs, in particular with respect to the independent modulation of the tunnel barrier transparencies, remains challenging and is typically addressed using electrostatic gating. We investigate charge transport in back-gated graphene mechanical break junctions and reveal Coulomb blockade physics characteristic of a single, high-quality QD when a nanogap is opened in a graphene constriction. By mechanically controlling the distance across the newly formed graphene nanogap, we achieve reversible tunability of the tunnel coupling to the drain electrode by 5 orders of magnitude, while keeping the source-QD tunnel coupling constant. The break junction device can therefore become a powerful platform to study the physical parameters that are crucial to the development of future graphene-based devices, including energy converters and quantum calorimeters., S.C. acknowledges a Marie Skłodowska-Curie Individual Fellowship under grant BioGraphING (ID: 798851) and P.G. acknowledges a Marie Skłodowska-Curie Individual Fellowship under grant TherSpinMol (ID: 748642) from the European Union’s Horizon 2020 research and innovation programme. K.W. and T.T. acknowledge support from the Elemental Strategy Initiative conducted by the MEXT, Japan, and the CREST (JPMJCR15F3), JST. This work was supported by the Graphene Flagship (a European Union’s Horizon 2020 research and innovation programme under grant agreement no. 649953), the Marie Curie ITN MOLESCO, an ERC advanced grant (Mols@Mols no. 240299), and a Spanish MCIU/AEI/FEDER project (PGC2018-094783).

In recent years, a wide range of single-molecule devices has been realized, enabled by technological advances combined with the versatility offered by synthetic chemistry. In particular, single-molecule diodes have attracted significant attention with an ongoing effort to increase the rectification ratio between the forward and reverse current. Various mechanisms have been investigated to improve rectification, either based on molecule-intrinsic properties or by engineering the coupling of the molecule to the electrodes. In this perspective, we first provide an overview of the current experimental approaches reported in literature to achieve rectification at the single-molecule level. We then proceed with our recent efforts in this direction, exploiting the internal structure of multi-site molecules, yielding the highest rectification ratio based on a molecule-intrinsic mechanism. We introduce the theoretical framework for multi-site molecules and infer general design guidelines from this. Based on these guidelines, a series of two-site molecules have been developed and integrated into devices. Using two- and three-terminal mechanically controllable break junction measurements, we show that depending on the on-site energies, which are tunable by chemical design, the devices either exhibit pronounced negative differential conductance, or behave as highly-efficient rectifiers. Finally, we propose a design of a single-molecule diode with a theoretical rectification ratio exceeding a million.

By studying transport through seven structurally related porphyrin derivatives with a machine learning algorithm we could identify and distinguish three different electronic paths., Porphyrin derivatives are key components in natural machinery enabling us to store sunlight as chemical energy. In spite of their prominent role in cascades separating electrical charges and their potential as sensitizers in molecular devices, reports concerning their electronic transport characteristics are inconsistent. Here we report a systematic investigation of electronic transport paths through single porphyrin junctions. The transport through seven structurally related porphyrin derivatives was repeatedly measured in an automatized mechanically controlled break-junction set-up and the recorded data were analyzed by an unsupervised clustering algorithm. The correlation between the appearances of similar clusters in particular sub-sets of the porphyrins with a common structural motif allowed us to assign the corresponding current path. The small series of model porphyrins allowed us to identify and distinguish three different electronic paths covering more than four orders of magnitude in conductance.

In transition metal dichalcogenides, defects have been found to play an important role, affecting doping, spin-valley relaxation dynamics, and assisting in proximity effects of spin-orbit coupling. Here, we study localized states in $\mathrm{WS}_2$ and how they affect tunneling through van der Waals heterostructures of h-BN/graphene/$\mathrm{WS}_2$/metal. The obtained conductance maps as a function of bias and gate voltage reveal single-electron transistor behavior (Coulomb blockade) with a rich set of transport features including excited states and negative differential resistance regimes. Applying a perpendicular magnetic field, we observe a shift in the energies of the quantum levels and information about the orbital magnetic moment of the localized states is extracted.

In two-dimensional materials research, oxidation is usually considered as a common source for the degradation of electronic and optoelectronic devices or even device failure. However, in some cases a controlled oxidation can open the possibility to widely tune the band structure of 2D materials. In particular, we demonstrate the controlled oxidation of titanium trisulfide (TiS3), a layered semiconductor that attracted much attention recently thanks to its quasi-1D electronic and optoelectronic properties and its direct bandgap of 1.1 eV. Heating TiS3 in air above 300 °C gradually converts it into TiO2, a semiconductor with a wide bandgap of 3.2 eV with applications in photo-electrochemistry and catalysis. In this work, we investigate the controlled thermal oxidation of individual TiS3 nanoribbons and its influence on the optoelectronic properties of TiS3-based photodetectors. We observe a step-wise change in the cut-off wavelength from its pristine value ~1000 nm to 450 nm after subjecting the TiS3 devices to subsequent thermal treatment cycles. Ab-initio and many-body calculations confirm an increase of the bandgap of titanium oxysulfide (TiO2-xSx) when increasing the amount of oxygen and reducing the amount of sulfur.

Phase engineering of MoS2 transistors has recently been demonstrated and has led to record low contact resistances. The phase patterning of MoS2 flakes with laser radiation has also been realized via spectroscopic methods, which invites the potential of controlling the metallic and semiconducting phases of MoS2 transistors by simple light exposure. Nevertheless, the fabrication and demonstration of laser-patterned MoS2 devices starting from the metallic polymorph have not been demonstrated yet. Here, we study the effects of laser radiation on 1T/1 $\mathrm{T}^{\prime }$ -MoS2 transistors with the prospect of driving an in situ phase transition to the 2H-polymorph through light exposure. We find that although the Raman peaks of 2H-MoS2 become more prominent and the ones from the 1T/1 $\mathrm{T}^{\prime }$ phase fade after the laser exposure, the semiconducting properties of the laser-patterned devices are not fully restored, and the laser treatment ultimately leads to the degradation of the transport channel.

The appealing feature of molecular electronics is the possibility of exploiting functionality built within a single molecule. This functionality can be employed, for example, for sensing or switching purposes. Thus, ideally, the associated conductance changes should be sizable upon application of external stimuli. Here, we show that a molecular spring can be mechanically compressed or elongated to tune its conductance by up to an order of magnitude by controlling the quantum interference between electronic pathways. Oscillations in the conductance occur when the stress built up in the molecule is high enough to allow the anchoring groups to move along the surface in a stick-slip-like fashion. The mechanical control of quantum interference effects and the resulting large change in molecular conductance open the door for applications in, e.g., a minute mechanosensitive sensing device functional at room temperature., 23 pages, 6 figures

In the field of nanomechanics, parametric excitations are of interest since they can greatly enhance sensing capabilities and eliminate cross-talk. Above a certain threshold of the parametric pump, the mechanical resonator can be brought into parametric resonance. Here we demonstrate parametric resonance of suspended single-layer graphene membranes by an efficient opto-thermal drive that modulates the intrinsic spring constant. With a large amplitude of the optical drive, a record number of 14 mechanical modes can be brought into parametric resonance by modulating a single parameter: the pre-tension. A detailed analysis of the parametric resonance allows us to study nonlinear dynamics and the loss tangent of graphene resonators. It is found that nonlinear damping, of the van der Pol type, is essential to describe the high amplitude parametric resonance response in atomically thin membranes.

Recent research in two-dimensional (2D) materials has boosted a renovated interest in the p-n junction, one of the oldest electrical components which can be used in electronics and optoelectronics. 2D materials offer remarkable flexibility to design novel p-n junction device architectures, not possible with conventional bulk semiconductors. In this Review we thoroughly describe the different 2D p-n junction geometries studied so far, focusing on vertical (out-of-plane) and lateral (in-plane) 2D junctions and on mixed-dimensional junctions. We discuss the assembly methods developed to fabricate 2D p-n junctions making a distinction between top-down and bottom-up approaches. We also revise the literature studying the different applications of these atomically thin p-n junctions in electronic and optoelectronic devices. We discuss experiments on 2D p-n junctions used as current rectifiers, photodetectors, solar cells and light emitting devices. The important electronics and optoelectronics parameters of the discussed devices are listed in a table to facilitate their comparison. We conclude the Review with a critical discussion about the future outlook and challenges of this incipient research field., Review, 34 pages, 11 figures, 4 tables

Owing to their atomic-scale thickness, the resonances of two-dimensional (2D) material membranes show signatures of nonlinearities at forces of only a few picoNewtons. Although the linear dynamics of membranes is well understood, the exact relation between the nonlinear response and the resonator’s material properties has remained elusive. Here we show a method for determining the Young’s modulus of suspended 2D material membranes from their nonlinear dynamic response. To demonstrate the method, we perform measurements on graphene and MoS2 nanodrums electrostatically driven into the nonlinear regime at multiple driving forces. We show that a set of frequency response curves can be fitted using only the cubic spring constant as a fit parameter, which we then relate to the Young’s modulus of the material using membrane theory. The presented method is fast, contactless, and provides a platform for high-frequency characterization of the mechanical properties of 2D materials., The mechanical resonances of atomically thin membranes show nonlinear responses at driving forces in the picoNewton range. Here, the authors develop a contactless method to extract the Young’s modulus of 2D materials from the nonlinear dynamic response of these nanomechanical resonators.

We present experimental and theoretical studies of single-molecule conductance through nonplanar fullerocurcuminoid molecular dyads in ambient conditions using the mechanically controllable break junction technique. We show that molecular dyads with bare fullerenes form configurations with conductance features related to different transport channels within the molecules, as identified with filtering and clustering methods. The primary channel corresponds to charge transport through the methylthio-terminated backbone. Additional low-conductance channels involve one backbone side and the fullerene. In fullerenes with four additional equatorial diethyl malonate groups attached to them, the latter transport pathway is blocked. Density functional theory calculations corroborate the experimental observations. In combination with nonequilibrium green functions, the conductance values of the fullerocurcuminoid backbones are found to be similar to those of a planar curcuminoid molecule without a fullerene attached. In the nonplanar fullerocurcuminoid systems, the highest-conductance peak occurs partly through space, compensating for the charge delocalization loss present in the curcuminoid system., Financial support from the European Commission (COST Action MOLSPIN CA15128 and EU RISE (DAFNEOX) project SEP-210165479) is gratefully acknowledged. The work at the University of Chile was supported by Fondecyt Regular Project 1181080 (D.D.), Fondecyt Regular Project 1161775 (M.S.), Fondecyt Regular Project 1170524 (D.A.), and Fondequip EQM140055 and EQM180009 (D.D). Powered@NLHPC: this research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). E.R. acknowledges MICIIN for grant PGC2018-093863-B-C21 and the Maria de Maeztu Excellence grant MDM-2017-0767, for the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputing Centre and CSUC and to the Generalitat de Catalunya for an ICREA Academia award and grant 2017SGR1289. H.S.J.v.d.Z. acknowledges support from the Dutch Science foundation (NWO). N.A.-A. thanks MEC for grant MAT2016-77852-C2-1-R, to the Generalitat de Catalunya for the grant 2017SGR1277, and the Severo Ochoa Program for Centers of Excellence in R&D (SEV-2015-0496). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement 724981). L.E. thanks the US National Science Foundation (NSF) for generous support of this work under the CHE-1801317 program. The Robert A. Welch Foundation is also gratefully acknowledged for an endowed chair to L.E. (grant AH-0033).

Recent experiments have shown surprisingly large thermal time constants in suspended graphene ranging from 10 to 100 ns in drums with a diameter ranging from 2 to 7 microns. The large time constants and their scaling with diameter points towards a thermal resistance at the edge of the drum. However, an explanation of the microscopic origin of this resistance is lacking. Here, we show how phonon scattering at a kink in the graphene, e.g. formed by sidewall adhesion at the edge of the suspended membrane, can cause a large thermal time constant. This kink strongly limits the fraction of flexural phonons that cross the suspended graphene edge, which causes a thermal interface resistance at its boundary. Our model predicts thermal time constants that are of the same order of magnitude as experimental data, and shows a similar dependence on the circumference. Furthermore, the model predicts the relative in-plane and out-of-plane phonon contributions to graphene's thermal expansion force, in agreement with experiments. We thus show, that in contrast to conventional thermal (Kapitza) resistance which occurs between two different materials, in 2D materials another type of thermal interface resistance can be geometrically induced in a single material.

The high flexibility, impermeability and strength of graphene membranes are key properties that can enable the next generation of nanomechanical sensors. However, for capacitive pressure sensors, the sensitivity offered by a single suspended graphene membrane is too small to compete with commercial sensors. Here, we realize highly sensitive capacitive pressure sensors consisting of arrays of nearly ten thousand small, freestanding double-layer graphene membranes. We fabricate large arrays of small-diameter membranes using a procedure that maintains the superior material and mechanical properties of graphene, even after high-temperature annealing. These sensors are readout using a low-cost battery-powered circuit board, with a responsivity of up to $$47.8$$ aF Pa−1 mm−2, thereby outperforming the commercial sensors. Arrays of tiny graphene membranes exhibit excellent performance as pressure sensors, offering a competitive, low-cost alternative to commercially available systems. Graphene offers a durable and resilient material for sensors that generate a capacitive readout to pressure changes, but individual membranes are not sufficiently sensitive. Researchers led by Makars Siskins and Peter Steeneken of the Delft University of Technology in the Netherlands have devised a strategy for fabricating graphene sensor arrays that overcome this limitation. Their method yields millimeter-scale assemblies of 10,000 double-layered graphene membranes, which can in turn be connected to an inexpensive battery-powered circuit board. The authors demonstrate that this system can outperform a state-of-the-art commercial pressure sensor, and propose that further improvements to the design and fabrication of these arrays could improve their responsiveness by a full order of magnitude.

We fabricate paper-supported semiconducting devices by rubbing a layered molybdenum disulfide (MoS2) crystal onto a piece of paper, similarly to the action of drawing/writing with a pencil on paper. We show that the abrasion between the MoS2 crystal and the paper substrate efficiently exfoliates the crystals, breaking the weak van der Waals interlayer bonds and leading to the deposition of a film of interconnected MoS2 platelets. Employing this simple method, that can be easily extended to other 2D materials, we fabricate MoS2-on-paper broadband photodectectors with spectral sensitivity from the ultraviolet (UV) to the near-infrared (NIR). We also used these paper-based photodetectors to acquire pictures of objects by mounting the photodetectors in a homebuilt single-pixel camera setup., Comment: 6 main text figures + 4 Supp Info figures

This is the post-peer reviewed version of the following article: Papadopoulos, Nikos et al. “Multi-terminal electronic transport in boron nitride encapsulated TiS3 nanosheets”. 2D Matererials, 2019, 7(1) 015009 doi:10.1088/2053-1583/ab4ef3 Which has been published in final form at: https://iopscience.iop.org/article/10.1088/2053-1583/ab4ef3, We have studied electrical transport as a function of carrier density, temperature and bias in multi-terminal devices consisting of hexagonal boron nitride (h-BN) encapsulated titanium trisulfide (TiS3) sheets. Through the encapsulation with h-BN, we observe metallic behavior and high electron mobilities. Below ∼60 K an increase in the resistance, and non-linear transport with plateau-like features in the differential resistance are present, in line with the expected charge density wave (CDW) formation. Importantly, the critical temperature and the threshold field of the CDW phase can be controlled through the back-gate, This work is in part financed by the Organization for Scientific Research (NWO) and the Ministry of Education, Culture, and Science (OCW). Growth of hexagonal boron nitride crystals was supported by the Elemental Strategy Initiative conducted by the MEXT, Japan and the CREST (JPMJCR15F3), JST. MIRE Group thanks the financial support from MINECO-FEDER through the project MA2015-65203-R

$${\hbox {SrIrO}}_{3}$$ SrIrO 3 , the three-dimensional member of the Ruddlesden–Popper iridates, is a paramagnetic semimetal characterised by a the delicate interplay between spin–orbit coupling and Coulomb repulsion. In this work, we study the anisotropic magnetoresistance (AMR) of $${\hbox {SrIrO}}_{3}$$ SrIrO 3 thin films, which is closely linked to spin–orbit coupling and probes correlations between electronic transport, magnetic order and orbital states. We show that the low-temperature negative magnetoresistance is anisotropic with respect to the magnetic field orientation, and its angular dependence reveals the appearance of a fourfold symmetric component above a critical magnetic field. We show that this AMR component is of magnetocrystalline origin, and attribute the observed transition to a field-induced magnetic state in $${\hbox {SrIrO}}_{3}$$ SrIrO 3 .

On-chip temperature sensing on a micro- to nanometer scale is becoming more desirable as the complexity of nanodevices and size requirements increase and with it the challenges in thermal probing and management. This highlights the need for scalable and reliable temperature sensors which have the potential to be incorporated into current and future device structures. Here, we show that U-shaped graphene stripes consisting of one wide and one narrow leg form a single material thermocouple that can function as a self-powering temperature sensor. We find that the graphene thermocouples increase in sensitivity with a decrease in leg width, due to a change in the Seebeck coefficient, which is in agreement with our previous findings and report a maximum sensitivity of $\Delta S \approx$ 39 $\mathrm{\mu}$V/K., Comment: 7 pages, 4 figures

Franckeite is a naturally occurring layered mineral with a structure composed of alternating stacks of SnS2-like and PbS-like layers. Although this superlattice is composed of a sequence of isotropic two-dimensional layers, it exhibits a spontaneous rippling that makes the material structurally anisotropic. We demonstrate that this rippling comes hand in hand with an inhomogeneous in-plane strain profile and anisotropic electrical, vibrational and optical properties. We argue that this symmetry breakdown results from a spatial modulation of the van der Waals interaction between layers due to the SnS2-like and PbS-like lattices incommensurability., Comment: 6 main text figures, Supp. Info. available upon request

In two-dimensional materials research, oxidation is usually considered as a common source for the degradation of electronic and optoelectronic devices or even device failure. However, in some cases a controlled oxidation can open the possibility to widely tune the band structure of 2D materials. In particular, we demonstrate the controlled oxidation of titanium trisulfide (TiS3), a layered semicon-ductor that has attracted much attention recently thanks to its quasi-1D electronic and optoelectron-ic properties and its direct bandgap of 1.1 eV. Heating TiS3 in air above 300 °C gradually converts it into TiO2, a semiconductor with a wide bandgap of 3.2 eV with applications in photo-electrochemistry and catalysis. In this work, we investigate the controlled thermal oxidation of indi-vidual TiS3 nanoribbons and its influence on the optoelectronic properties of TiS3-based photodetec-tors. We observe a step-wise change in the cut-off wavelength from its pristine value ~1000 nm to 450 nm after subjecting the TiS3 devices to subsequent thermal treatment cycles. Ab-initio and many-body calculations confirm an increase in the bandgap of titanium oxysulfide (TiO2-xSx) when in-creasing the amount of oxygen and reducing the amount of sulfur.

Two-dimensional layered trichalcogenide materials have recently attracted the attention of the scientific community because of their robust mechanical and thermal properties and applications in opto- and nanoelectronics devices. We report the pressure dependence of out-of-plane Ag Raman modes in high quality few-layer titanium trisulfide (TiS3) nanoribbons grown using a direct solid-gas reaction method and infer their cross-plane thermal expansion coefficient. Both mechanical stability and thermal properties of the TiS3 nanoribbons are elucidated by using phonon-spectrum analyses. Raman spectroscopic studies at high pressure (up to 34 GPa) using a diamond anvil cell identify four prominent Ag Raman bands; a band at 557 cm-1 softens under compression, and others at 175, 300, and 370 cm-1 show normal hardening. Anomalies in phonon mode frequencies and excessive broadening in line width of the soft phonon about 13 GPa are attributed to the possible onset of a reversible structural transition. A complete structural phase transition at 43 GPa is inferred from the Ag soft mode frequency (557 cm-1) versus pressure extrapolation curve, consistent with recently reported theoretical predictions. Using the experimental mode Grüneisen parameters γi of Raman modes, we estimated the cross-plane thermal expansion coefficient Cv of the TiS3 nanoribbons at ambient phase to be 1.321 × 10-6 K-1. The observed results are expected to be useful in calibration and performance of next-generation nanoelectronics and optical devices under extreme stress conditions.

Paper based thermoresistive sensors are fabricated by rubbing WS2 powder against a piece of standard copier paper, like the way a pencil is used to write on paper. The abrasion between the layered material and the rough paper surface erodes the material, breaking the weak van der Waals interlayer bonds, yielding a film of interconnected platelets. The resistance of WS2 presents a strong temperature dependence, as expected for a semiconductor material in which charge transport is due to thermally activated carriers. This strong temperature dependence makes the paper supported WS2 devices extremely sensitive to small changes in temperature. This exquisite thermal sensitivity, and their fast response times to sudden temperature changes, is exploited thereby demonstrating the usability of a WS2-on-paper thermal sensor in a respiration monitoring device., 6 main text figures, 1 table, 6 supp. info. figures

Strain engineering is one of the most effective approaches to manipulate the physical state of materials, control their electronic properties, and enable crucial functionalities. Because of their rich phase diagrams arising from competing ground states, quantum materials are an ideal playground for on-demand material control and can be used to develop emergent technologies, such as adaptive electronics or neuromorphic computing. It was recently suggested that complex oxides could bring unprecedented functionalities to the field of nanomechanics, but the possibility of precisely controlling the stress state of materials is so far lacking. Here, we demonstrate the wide and reversible manipulation of the stress state of single-crystal WO

We report on the fabrication and measurements of platinum-self-aligned nanogap devices containing cubed iron (core)/iron oxide (shell) nanoparticles (NPs) with two average different sizes (13 and 17 nm). The nanoparticles are deposited by means of a cluster gun technique. Their trapping across the nanogap is demonstrated by comparing the current vs voltage characteristics (I-Vs) before and after the deposition. At low temperature, the I-Vs can be well fitted to the Korotkov and Nazarov Coulomb blockade model, which captures the coexistence of single-electron tunneling and tunnel barrier suppression upon a bias voltage increase. The measurements thus show that Coulombblockaded devices can be made with a nanoparticle cluster source, which extends the existing possibilities to fabricate such devices to those in which it is very challenging to reduce the usual NP agglomeration given by a solution method., This study was supported by the EU Horizon 2020 research and innovation program under the Marie-Sklodowska-Curie Grant Agreement No. 645658 (DAFNEOX Project), by two FONDECYT REGULAR Grant Nos. 1181080 and 1161775, and by two FONDEQUIP Grant Nos. EQM140055 and EQM180009. We thank the Spanish Ministry of Science, Innovation and Universities (Project Nos. MAT2015-71664-R and RTI2018-099960-B-I00) and the Serbian Ministry of Education, Science and Technological Development (Project No. III45018) for their support. A.P. and Z.K. thank Senzor-INFIZ (Serbia) for the cooperation provided during their respective secondments.

Porphyrin derivatives are key components in natural machinery enabling us to store sunlight as chemical energy. In spite of their prominent role in cascades separating electrical charges and their potential as sensitizers in molecular devices, reports concerning their electronic transport characteristics are inconsistent. Here we report a systematic investigation of electronic transport paths through single porphyrin junctions. The transport through seven structurally related porphyrin derivatives was repeatedly measured in an automatized mechanically controlled break-junction set-up and the recorded data were analyzed by an unsupervised clustering algorithm. The correlation between the appearances of similar clusters in particular sub-sets of the porphyrins with a common structural motif allowed us to assign the corresponding current path. The small series of model porphyrins allowed us to identify and distinguish three different electronic paths covering more than four orders of magnitude in conductance.

A new concept to improve the reliability of functional single molecule junctions is presented using the E-field triggered switching of FeIIbis-terpyridine complexes in a mechanically controlled break junction experiment as model system. The complexes comprise a push-pull ligand sensing the applied E-field and the resulting distortion of the FeII ligand field is expected to trigger a spin-crossover event reflected in a sudden jump of the transport current. By molecular engineering, the active centre of the complex is separated from the gold electrodes in order to eliminate undesired side-effects. Two aspects are considered to isolate the central metal ion, namely the spacing by introducing additional alkynes, and the steric shielding achieved by bulky isopropyl groups. With this small series of model complexes, a pronounced correlation is observed between the occurrence of bistable junctions and the extent of separation of the central metal ion, affirming the hypothesized Enhanced Separation Concept (ESC). &nbsp

We present measurements of weak localization on hexagonal boron nitride encapsulated bilayer ${\mathrm{MoS}}_{2}$. From the analysis we obtain information regarding the phase coherence and the spin diffusion of the electrons. We find that the encapsulation with boron nitride provides higher mobilities in the samples, and the phase coherence shows improvement, while the spin relaxation does not exhibit any significant enhancement compared to nonencapsulated ${\mathrm{MoS}}_{2}$. The spin relaxation time is in the order of a few picoseconds, indicating a fast intravalley spin-flip rate. Lastly, the spin-flip rate is found to be independent from electron density in the current range, which can be explained through counteracting spin-flip scattering processes based on electron-electron Coulomb scattering and extrinsic Bychkov-Rashba spin-orbit coupling.

Development of molecules that can switch between redox states with paired and unpaired electrons is important for molecular electronics and spintronics. In this work, a selection of redox-active indenofluorene-extended tetrathiafulvalenes (IF-TTFs) with thioacetate end groups was prepared from a readily obtainable dibromo-functionalized IF-TTF building block using palladium-catalyzed cross-coupling reactions, such as the Suzuki reaction. The end groups served as electrode anchoring groups for single-molecule conductance studies, and the molecules were subjected to mechanically controlled break-junction measurements with gold contacts and to low-bias charge transport measurements in gated three-terminal electromigration junctions. The neutral molecules showed clear conductance signatures, and somewhat surprisingly, we found that a meta-meta anchoring configuration gave a higher conductance than a para-meta configuration. We explain this behavior by "through-space" coupling between the gold electrode and the phenyl on which the anchoring group is attached. Upon charging the molecule in a gated junction, we found reproducibly a Kondo effect (zero-bias conductance) attributed to a net spin. Ready generation of radical cations was supported by cyclic voltammetry measurements, revealing stepwise formation of radical cation and dication species in solution. The first oxidation event was accompanied by association reactions as the appearance of the first oxidation peak was strongly concentration dependent.

Recent observations of destructive quantum interference in single-molecule junctions confirm the role played by quantum effects in the electronic conductance properties of molecular systems. We show here that the destructive interference can be turned ON or OFF within the same molecular system by mechanically controlling its conformation. Using a combination of ab-initio calculations and single-molecule conductance measurements, we demonstrate the existence of a quasi-periodic destructive quantum interference pattern along the breaking traces of {\pi}-{\pi} stacked molecular dimers. The detection of these interferences, which are due to opposite signs of the intermolecular electronic couplings, was only made possible by a combination of wavelet transform and higher-order statistical analysis of single-breaking traces. The results demonstrate that it is possible to control the molecular conductance over a few orders of magnitudes and with a sub-angstrom resolution by exploiting the subtle structure-property relationship of {\pi}-{\pi} stack dimers. These large conductance changes may be beneficial for the design of single-molecule electronic components that exploit the intrinsic quantum effects occurring at the molecular scale., Comment: 10 pages, 4 figures

We report on an approach to realize carbon-gold (C-Au) bonded molecular junctions without the need for an additive to deprotect the alkynyl carbon as endstanding anchor group. Using the mechanically controlled break junction (MCBJ) technique, we determine the most probable conductance value of a family of alkynyl terminated oligophenylenes (OPA(n)) connected to gold electrodes through such an akynyl moiety in ambient conditions. The molecules bind to the gold leads through an sp-hybridized carbon atom at each side. Comparing our results with other families of molecules that present organometallic C-Au bonds, we conclude that the conductance of molecules contacted via an sp-hybridized carbon atom is lower than the ones using sp(3) hybridization due to strong differences in the coupling of the conducting orbitals with the gold leads.

The charge transport properties of SCO [Fe(Htrz)2 (trz)](BF4 ) NPs covered with a silica shell placed in between single-layer graphene electrodes are reported. A reproducible thermal hysteresis loop in the conductance above room-temperature is evidenced. This bistability combined with the versatility of graphene represents a promising scenario for a variety of technological applications but also for future sophisticated fundamental studies.

Single-molecule break-junction measurements are intrinsically stochastic in nature, requiring the acquisition of large datasets of “breaking traces” to gain insight into the generic electronic properties of the molecule under study. For example, the most probable conductance value of the molecule is often extracted from the conductance histogram built from these traces. In this letter, we present an unsupervised and reference-free machine learning tool to improve the determination of the conductance of oligo(phenylene ethynylene)dithiol from mechanically controlled break-junction (MCBJ) measurements. Our method allows for the classification of individual breaking traces based on an image recognition technique. Moreover, applying this technique to multiple merged datasets makes it possible to identify common breaking behaviors present across different samples, and therefore to recognize global trends. In particular, we find that the variation in the extracted molecular conductance can be significantly reduced resulting in a more reliable estimation of molecular conductance values from MCBJ datasets. Finally, our approach can be more widely applied to different measurement types which can be converted to two-dimensional images.

Physical review research 2(1), 012058 (2020). doi:10.1103/PhysRevResearch.2.012058, Published by APS, College Park, MD

The energy dependent thermoelectric response of a single molecule contains valuable information about its transmission function and its excited states. However, measuring it requires devices that can efficiently heat up one side of the molecule while being able to tune its electrochemical potential over a wide energy range. Furthermore, to increase junction stability, devices need to operate at cryogenic temperatures. In this work, we report on a device architecture to study the thermoelectric properties and the conductance of single molecules simultaneously over a wide energy range. We employ a sample heater in direct contact with the metallic electrodes contacting the single molecule which allows us to apply temperature biases up to ΔT = 60 K with minimal heating of the molecular junction. This makes these devices compatible with base temperatures Tbath < 2 K and enables studies in the linear ( Δ T ≪ T molecule) and nonlinear ( Δ T ≫ T molecule) thermoelectric transport regimes.The energy dependent thermoelectric response of a single molecule contains valuable information about its transmission function and its excited states. However, measuring it requires devices that can efficiently heat up one side of the molecule while being able to tune its electrochemical potential over a wide energy range. Furthermore, to increase junction stability, devices need to operate at cryogenic temperatures. In this work, we report on a device architecture to study the thermoelectric properties and the conductance of single molecules simultaneously over a wide energy range. We employ a sample heater in direct contact with the metallic electrodes contacting the single molecule which allows us to apply temperature biases up to ΔT = 60 K with minimal heating of the molecular junction. This makes these devices compatible with base temperatures Tbath < 2 K and enables studies in the linear ( Δ T ≪ T molecule) and nonlinear ( Δ T ≫ T molecule) thermoelectric transport regimes.

The bowl-shaped, 3-fold interlinked porphyrin dimer 2 was obtained in respectable yields during macrocyclization attempts. Its bicyclic structure, consisting of a macrocycle made of a pair of acetylene interlinked tetraphenylporphyrins which are additionally linked by a C-C bond interlinking two pyrrole subunits, has been confirmed spectroscopically (2D-NMR, UV/vis, HR-MALDI-ToF MS). Late-stage functionalization provided the structural analogue 1 with acetyl-protected terminal thiol anchor groups enabling single molecule transport investigations in a mechanically controlled break junction experiment. The formation of single-molecule junctions was observed, displaying large variations in the observed conductance values pointing at a rich diversity in the molecular junctions.

Two-dimensional (2D) materials with strong in-plane anisotropy are of interest for enabling orientation-dependent, frequency-tunable, optomechanical devices. However, black phosphorus (bP), the 2D material with the largest anisotropy to date, is unstable as it degrades in air. In this work we show that As2S3 is an interesting alternative, with a similar anisotropy to bP, while at the same time having a much higher chemical stability. We probe the mechanical and optical anisotropy in As2S3 by three distinct angular-resolved experimental methods: Raman spectroscopy, atomic force microscopy (AFM), and resonance frequency analysis. Using a dedicated angle-resolved AFM force-deflection method, an in-plane anisotropy factor of EaEc=1.7 is found in the Young's modulus of As2S3 with Ea-axis = 79.1 ± 10.1 GPa and Ec-axis = 47.2 ± 7.9 GPa. The high mechanical anisotropy is also shown to cause up to 65% difference in the resonance frequency, depending on crystal orientation and aspect ratio of membranes.

Current wafer-scale fabrication methods for graphene-based electronics and sensors involve the transfer of single-layer graphene by a support polymer. This often leaves some polymer residue on the graphene, which can strongly impact its electronic, thermal, and mechanical resonance properties. To assess the cleanliness of graphene fabrication methods, it is thus of considerable interest to quantify the amount of contamination on top of the graphene. Here, we present a methodology for the direct measurement of the mass of the graphene sheet using quartz crystal microbalances (QCMs). By monitoring the QCM resonance frequency during removal of graphene in an oxygen plasma, the total mass of the graphene and contamination is determined with sub-graphene-monolayer accuracy. Since the etch-rate of the contamination is higher than that of graphene, quantitative measurements of the mass of contaminants below, on top, and between graphene layers are obtained. We find that polymer-based dry transfer methods can increase the mass of a graphene sheet by a factor of 10. The presented mass measurement method is conceptually straightforward to interpret and can be used for standardized testing of graphene transfer procedures in order to improve the quality of graphene devices in future applications.

A new concept to improve the reliability of functional single molecule junctions is presented using the E-field triggered switching of FeIIbis-terpyridine complexes in a mechanically controlled break junction experiment as model system. The complexes comprise a push-pull ligand sensing the applied E-field and the resulting distortion of the FeII ligand field is expected to trigger a spin-crossover event reflected in a sudden jump of the transport current. By molecular engineering, the active centre of the complex is separated from the gold electrodes in order to eliminate undesired side-effects. Two aspects are considered to isolate the central metal ion, namely the spacing by introducing additional alkynes, and the steric shielding achieved by bulky isopropyl groups. With this small series of model complexes, a pronounced correlation is observed between the occurrence of bistable junctions and the extent of separation of the central metal ion, affirming the hypothesized Enhanced Separation Concept (ESC).

Graphene's maximized surface‐to‐volume ratio, high conductance, mechanical strength, and flexibility make it a promising nanomaterial. However, large‐scale graphene production is typically cost‐intensive. This manuscript describes a microbial reduction approach for producing graphene that utilizes the bacterium Shewanella oneidensis in combination with modern nanotechnology to enable a low‐cost, large‐scale production method. The bacterial reduction approach presented in this paper increases the conductance of single graphene oxide flakes as well as bulk graphene oxide sheets by 2.1 to 2.7 orders of magnitude respectively while simultaneously retaining a high surface‐area‐to‐thickness ratio. Shewanella‐mediated reduction was employed in conjunction with electron‐beam lithography to reduce one surface of individual graphene oxide flakes. This methodology yielded conducting flakes with differing functionalization on the top and bottom faces. Therefore, microbial reduction of graphene oxide enables the development and up‐scaling of new types of graphene‐based materials and devices with a variety of applications including nano‐composites, conductive inks, and biosensors, while avoiding usage of hazardous, environmentally‐unfriendly chemicals.

We investigate theoretically and experimentally the singlet-triplet Kondo effect induced by a magnetic field in a molecular junction. Temperature dependent conductance, $G(T)$, is calculated by the numerical renormalization group, showing a strong imprint of the relevant low energy scales, such as the Kondo temperature, exchange and singlet-triplet splitting. We demonstrate the stability of the singlet-triplet Kondo effect against weak spin anisotropy, modeled by an anisotropic exchange. Moderate spin anisotropy manifests itself by lowering the Kondo plateaus, causing the $G(T)$ to deviate from a standard temperature dependence, expected for a spin-half Kondo effect. We propose this scenario as an explanation for anomalous $G(T)$, measured in an organic diradical molecule coupled to gold contacts. We uncover certain new aspects of the singlet-triplet Kondo effect, such as coexistence of spin-polarization on the molecule with Kondo screening and non-perturbative parametric dependence of an effective magnetic field induced by the leads., 15 pages, 9 figures; invited contribution to the "Virtual Special Issue" in honor of Abraham Nitzan in The Journal of Physical Chemistry C; v2: minor updates to the text and figures, added 2 paragraphs on numerical values of model parameters

One of the main challenges to upscale the fabrication of molecular devices is to achieve a mechanically stable device with reproducible and controllable electronic features that operates at room temperature1,2. This is crucial because structural and electronic fluctuations can lead to significant changes in the transport characteristics at the electrode-molecule interface3,4. In this study, we report on the realization of a mechanically and electronically robust graphene-based molecular junction. Robustness was achieved by separating the requirements for mechanical and electronic stability at the molecular level. Mechanical stability was obtained by anchoring molecules directly to the substrate, rather than to graphene electrodes, using a silanization reaction. Electronic stability was achieved by adjusting the π-π orbitals overlap of the conjugated head groups between neighbouring molecules. The molecular devices exhibited stable current-voltage (I-V) characteristics up to bias voltages of 2.0 V with reproducible transport features in the temperature range from 20 to 300 K.

Nano letters 19(2), 1282-1288 (2019). doi:10.1021/acs.nanolett.8b04862, Published by ACS Publ., Washington, DC