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Although 2D materials hold great potential for next-generation pressure sensors, recent studies revealed that gases permeate along the membrane-surface interface that is only weakly bound by van der Waals interactions, necessitating additional sealing procedures. In this work, we demonstrate the use of free-standing complex oxides as self-sealing membranes that allow the reference cavity of pressure sensors to be sealed by a simple anneal. To test the hermeticity, we study the gas permeation time constants in nano-mechanical resonators made from SrRuO3 and SrTiO3 membranes suspended over SiO2/Si cavities which show an improvement up to 4 orders of magnitude in the permeation time constant after annealing the devices for 15 minutes. Similar devices fabricated on Si3N4/Si do not show such improvements, suggesting that the adhesion increase over SiO2 is mediated by oxygen bonds that are formed at the SiO2/complex oxide interface during the self-sealing anneal. We confirm the enhancement of adhesion by picosecond ultrasonics measurements which show an increase in the interfacial stiffness by 70% after annealing. Since it is straigthforward to apply, the presented self-sealing method is thus a promising route toward realizing ultrathin hermetic pressure sensors., 7 pages, 5 figures

Microphones exploit the motion of suspended membranes to detect sound waves. Since the microphone performance can be improved by reducing the thickness and mass of its sensing membrane, graphene-based microphones are expected to outperform state-of-the-art microelectromechanical (MEMS) microphones and allow further miniaturization of the device. Here, we present a laser vibrometry study of the acoustic response of suspended multilayer graphene membranes for microphone applications. We address performance parameters relevant for acoustic sensing, including mechanical sensitivity, limit of detection and nonlinear distortion, and discuss the trade-offs and limitations in the design of graphene microphones. We demonstrate superior mechanical sensitivities of the graphene membranes, reaching more than 2 orders of magnitude higher compliances than commercial MEMS devices, and report a limit of detection as low as 15 dBSPL, which is 10-15 dB lower than that featured by current MEMS microphones.

The possibility to study quantum interference phenomena at ambient conditions is an appealing feature of molecular electronics. By connecting two porphyrins in a cofacial cyclophane, we create an attractive platform for mechanically controlling electric transport through the intramolecular extent of π-orbital overlap of the porphyrins facing each other and through the angle of xanthene bridges with regard to the porphyrin planes. We analyze theoretically the evolution of molecular configurations in the pulling process and the corresponding changes in electric conduction by combining density functional theory (DFT) with Landauer scattering theory of phase-coherent elastic transport. Predicted conductances during the stretching process show order of magnitude variations caused by two robust destructive quantum interference features that span through the whole electronic gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Mechanically-controlled break junction (MCBJ) experiments at room temperature verify the mechanosensitive response of the molecular junctions. During the continuous stretching of the molecule, they show conductance variations of up to 1.5 orders of magnitude over single breaking events. Uncommon triple-and quadruple-frequency responses are observed in periodic electrode modulation experiments with amplitudes of up to 10 Å. This further confirms the theoretically predicted double transmission dips caused by the spatial and energetic rearrangement of molecular orbitals, with contributions from both through-space and through-bond transport. This journal is

Two-dimensional magnetic materials with strong magnetostriction are attractive systems for realizing strain-tuning of the magnetization in spintronic and nanomagnetic devices. This requires an understanding of the magneto-mechanical coupling in these materials. In this work, we suspend thin Cr2Ge2Te6 layers and their heterostructures, creating ferromagnetic nanomechanical membrane resonators. We probe their mechanical and magnetic properties as a function of temperature and strain by observing magneto-elastic signatures in the temperature-dependent resonance frequency near the Curie temperature, TC. We compensate for the negative thermal expansion coefficient of Cr2Ge2Te6 by fabricating heterostructures with thin layers of WSe2 and antiferromagnetic FePS3, which have positive thermal expansion coefficients. Thus we demonstrate the possibility of probing multiple magnetic phase transitions in a single heterostructure. Finally, we demonstrate a strain-induced enhancement of TC in a suspended Cr2Ge2Te6-based heterostructure by 2.5 ± 0.6 K by applying a strain of 0.026% via electrostatic force.

Suspended piezoelectric thin films are key elements enabling high-frequency filtering in telecommunication devices. To meet the requirements of next-generation electronics, it is essential to reduce device thickness for reaching higher resonance frequencies. Here, the high-quality mechanical and electrical properties of graphene electrodes are combined with the strong piezoelectric performance of the free-standing complex oxide, BaTiO3 (BTO), to create ultrathin piezoelectric resonators. It is demonstrated that the device can be brought into mechanical resonance by piezoelectric actuation. By sweeping the DC bias voltage on the top graphene electrode, the BTO membrane is switched between the two poled ferroelectric states. Remarkably, ferroelectric hysteresis is also observed in the resonance frequency, magnitude and Q-factor of the first membrane mode. In the bulk acoustic mode, the device vibrates at 233 GHz. This work demonstrates the potential of combining van der Waals materials with complex oxides for next-generation electronics, which not only opens up opportunities for increasing filter frequencies, but also enables reconfiguration by poling, via ferroelectric memory effect.

Despite theoretical predictions that graphene should be impermeable to all gases, practical experiments on sealed graphene nanodrums show small leak rates. Thus far, the exact mechanism for this permeation has remained unclear, because different potential leakage pathways have not been studied separately. Here, we demonstrate a sealing method that consists of depositing SiO2 across the edge of suspended multilayer graphene flakes using electron beam-induced deposition. By sealing, leakage along the graphene-SiO2 interface is blocked, which is observed to result in a reduction in permeation rate by a factor of 104. The experiments thus demonstrate that gas flow along the graphene-SiO2 interface tends to dominate the leak rate in unsealed graphene nanodrums. Moreover, the presented sealing method enables the study of intrinsic gas leakage through graphene membranes and can enable hermetic graphene membranes for pressure sensing applications.

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 WO3 by strain engineering controlled by catalytic hydrogenation. Progressive incorporation of hydrogen in freestanding ultra-thin structures determines large variations of their mechanical resonance frequencies and induces static deformation. Our results demonstrate hydrogen doping as a new paradigm to reversibly manipulate the mechanical properties of nanodevices based on materials control., 6 pages, 4 figures, 9 supplementary sections

Direct measurement of single-molecule electrical transparency by break junction experiments has become a major field of research over the two last decades. This review specifically and comprehensively highlights the use of porphyrins as molecular components and discusses their potential use for the construction of future devices. Throughout the review, the features provided by porphyrins, such as low level misalignments and very low attenuation factors, are shown with numerous examples, illustrating the potential and limitations of these molecular junctions, as well as differences emerging from applied integration/investigation techniques., Porphyrins have unique properties in electronic circuits. This review summarizes single molecule junction experiments and encourages the development of next generation molecular devices based on such building blocks.

Nano letters 21(18), 7617-7624 (2021). doi:10.1021/acs.nanolett.1c02237, Published by ACS Publ., Washington, DC

The dynamics of suspended two-dimensional (2D) materials has received increasing attention during the last decade, yielding new techniques to study and interpret the physics that governs the motion of atomically thin layers. This has led to insights into the role of thermodynamic and nonlinear effects as well as the mechanisms that govern dissipation and stiffness in these resonators. In this review, we present the current state-of-the-art in the experimental study of the dynamics of 2D membranes. The focus will be both on the experimental measurement techniques and on the interpretation of the physical phenomena exhibited by atomically thin membranes in the linear and nonlinear regimes. We will show that resonant 2D membranes have emerged both as sensitive probes of condensed matter physics in ultrathin layers, and as sensitive elements to monitor small external forces or other changes in the environment. New directions for utilizing suspended 2D membranes for material characterization, thermal transport, and gas interactions will be discussed and we conclude by outlining the challenges and opportunities in this upcoming field., Comment: 39 pages, 16 figures

Theoretical studies suggest that mastering the thermocurrent through single molecules can lead to thermoelectric energy harvesters with unprecedentedly high efficiencies.1,2,3,4,5,6This can be achieved by engineering molecule length,7optimizing the tunnel coupling strength of molecules via chemical anchor groups8or by creating localized states in the backbone with resulting quantum interference features.4Empirical verification of these predictions, however, faces considerable experimental challenges and is still awaited. Here we use a novel measurement protocol that simultaneously probes the conductance and thermocurrent flow as a function of bias voltage and gate voltage. We find that the resulting thermocurrent is strongly asymmetric with respect to the gate voltage, with evidence of molecular excited states in the thermocurrent Coulomb diamond maps. These features can be reproduced by a rate-equation model only if it accounts for both the vibrational coupling and the electronic degeneracies, thus giving direct insight into the interplay of electronic and vibrational degrees of freedom, and the role of spin entropy in single molecules. Overall these results show that thermocurrent measurements can be used as a spectroscopic tool to access molecule-specific quantum transport phenomena.

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

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).

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

Hexagonal boron nitride is a 2D material whose single-layer allotrope has not been intensively studied despite being the substrate for graphene electronics. Its transparency and stronger interlayer adhesion with respect to graphene makes it difficult to work with, and few applications have been proposed. We have developed a transfer technique for this extra-adhesive material that does not require its visual localization, and fabricated mechanical resonators made out of chemical vapor-deposited single-layer hexagonal boron nitride. The suspended material was initially contaminated with polymer residues from the transfer, and the devices showed an unexpected tensioning when cooling them to 3 K. After cleaning in harsh environments with air at 450 °C and ozone, the temperature dependence changed with f 0 Q products reaching 2 × 1010 Hz at room temperature. This work paves the way to the realization of highly sensitive mechanical systems based on hexagonal boron nitride, which could be used as an alternative material to SiN for optomechanics experiments at room temperature. An improved transfer method allows easy placement of highly transparent and strongly adhesive hexagonal boron nitride on target substrates. A team led by Santiago J. Cartamil-Bueno at Delft University of Technology developed a technique that enables the transfer of large-area, single-layer hexagonal boron nitride films grown by chemical vapor deposition onto a substrate of choice, whilst not requiring optical visualization. Following an additional cleaning step, the atomically thin membranes were transferred onto circular microcavities patterned on a silicon oxide substrate, resulting in the formation of suspended drums. Cleaning in harsh environments using a mixture of air and ozone is instrumental to a substantial improvement in the quality factor of the drums, indicating that undesired contamination causes damping of the mechanical motion. These results show promise for the development of sensitive hexagonal boron nitride resonators.

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

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

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.

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.

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

We use a scalable optical technique to characterize more than 21000 circular nanomechanical devices made out of suspended single- and double-layer graphene on cavities with different diameters ($D$) and depths ($g$). To maximize the contrast between suspended and broken membranes we used a model for selecting the optimal color filter. The method enables parallel and automatized image processing for yield statistics. We find the survival probability to be correlated to a structural mechanics scaling parameter given by $D^4/g^3$. Moreover, we extract a median adhesion energy of $\Gamma =$ 0.9 J/m$^2$ between the membrane and the native SiO$_2$ at the bottom of the cavities., Comment: 7 pages, 5 figures

We study single-molecule oligo(phenylene ethynylene)dithiol junctions by means of inelastic electron tunneling spectroscopy (IETS). The molecule is contacted with gold nano-electrodes formed with the mechanically controllable break junction technique. We record the IETS spectrum of the molecule from direct current measurements, both as a function of time and electrode separation. We find that for fixed electrode separation the molecule switches between various configurations, which are characterized by different IETS spectra. Similar variations in the IETS signal are observed during atomic rearrangements upon stretching of the molecular junction. Using quantum chemistry calculations, we identity some of the vibrational modes which constitute a chemical fingerprint of the molecule. In addition, changes can be attributed to rearrangements of the local molecular environment, in particular at the molecule–electrode interface. This study shows the importance of taking into account the interaction with the electrodes when describing inelastic contributions to transport through single-molecule junctions.

Controlling the strain in two-dimensional (2D) materials is an interesting avenue to tailor the mechanical properties of nanoelectromechanical systems. Here, we demonstrate a technique to fabricate ultrathin tantalum oxide nanomechanical resonators with large stress by the laser oxidation of nano-drumhead resonators composed of tantalum diselenide (TaSe2), a layered 2D material belonging to the metal dichalcogenides. Before the study of their mechanical properties with a laser interferometer, we verified the oxidation and crystallinity of the freely suspended tantalum oxide using high-resolution electron microscopy. We demonstrate that the stress of tantalum oxide resonators increases by 140 MPa (with respect to pristine TaSe2 resonators), which causes an enhancement in the quality factor (14 times larger) and resonance frequency (9 times larger) of these resonators.

We report on an experimental investigation of transport through single molecules, trapped between two gold nano-electrodes fabricated with the mechanically controlled break junction (MCBJ) technique. The four molecules studied share the same core structure, namely oligo(phenylene ethynylene) (OPE3), while having different aurophilic anchoring groups: thiol (SAc), methyl sulfide (SMe), pyridyl (Py) and amine (NH2). The focus of this paper is on the combined characterization of the electrical and mechanical properties determined by the anchoring groups. From conductance histograms we find that thiol anchored molecules provide the highest conductance; a single-level model fit to current–voltage characteristics suggests that SAc groups exhibit a higher electronic coupling to the electrodes, together with better level alignment than the other three groups. An analysis of the mechanical stability, recording the lifetime in a self-breaking method, shows that Py and SAc yield the most stable junctions while SMe form short-lived junctions. Density functional theory combined with non-equlibrium Green’s function calculations help in elucidating the experimental findings.

TiS3 nanosheets have proven to be promising candidates for ultrathin optoelectronic devices due to their direct narrow band-gap and the strong light-matter interaction. In addition, the marked in-plane anisotropy of TiS3 is appealing for the fabrication of polarization sensitive optoelectronic devices. Herein, we study the optical contrast of TiS3 nanosheets of variable thickness on SiO2/Si substrates, from which we obtain the complex refractive index in the visible spectrum. We find that TiS3 exhibits very large birefringence, larger than that of well-known strong birefringent materials like TiO2 or calcite, and linear dichroism. These findings are in qualitative agreement with ab initio calculations that suggest an excitonic origin for the birefringence and linear dichroism of the material.

Embedding a magnetic electroactive molecule in a three-terminal junction allows for the fast and local electric field control of magnetic properties desirable in spintronic devices and quantum gates. Here, we provide an example of this control through the reversible and stable charging of a single all-organic neutral diradical molecule. By means of inelastic electron tunnel spectroscopy we show that the added electron occupies a molecular orbital distinct from those containing the two radical electrons, forming a spin system with three antiferromagnetically coupled spins. Changing the redox state of the molecule therefore switches on and off a parallel exchange path between the two radical spins through the added electron. This electrically controlled gating of the intramolecular magnetic interactions constitutes an essential ingredient of a single-molecule quantum gate., We acknowledge financial support by the Dutch Organization for Fundamental Research (NWO/FOM), an advanced ERC grant (Mols@Mols), and The Netherlands Organisation for Scientific Research (NWO/OCW) as part of the Frontiers of Nanoscience program. E.B. acknowledges funds from the EU FP7 program through Project 618082 ACMOL and a NWOVENI fellowship. C.R. and J.V. are thankful for funds from Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBER-BBN), MINECO, Spain (CTQ2013-40480-R, CTQ 2016-80030-R, and ”Severo Ochoa” Programme for Centers of Excellence in R&D, SEV2015-0496), MCSA ITN Network i-Switch (GA 642196), and Generalitat de Catalunya (2014-SGR-17).

Spin-crossover (SCO) molecules are versatile magnetic switches with applications in molecular electronics and spintronics. Downscaling devices to the single-molecule level remains, however, a challenging task since the switching mechanism in bulk is mediated by cooperative intermolecular interactions. Here, we report on electron transport through individual Fe-SCO molecules coupled to few-layer graphene electrodes via π-π stacking. We observe a distinct bistability in the conductance of the molecule and a careful comparison with density functional theory (DFT) calculations allows to associate the bistability with a SCO-induced orbital reconfiguration of the molecule. We find long spin-state lifetimes that are caused by the specific coordination of the magnetic core and the absence of intermolecular interactions according to our calculations. In contrast with bulk samples, the SCO transition is not triggered by temperature but induced by small perturbations in the molecule at any temperature. We propose plausible mechanisms that could trigger the SCO at the single-molecule level., We acknowledge financial support from the Dutch Organization for Fundamental research (NWO/FOM), the European Commission through an advanced ERC grant (Mols@Mols) and the Marie Curie ITN MOLESCO, from the Netherlands Organization for Scientific Research (NWO/OCW) as part of the Frontiers of Nanoscience program, and from the Spanish Ministerio de Economia y Competitividad through the project FIS2015-63918-R. EB thanks funds from the EU FP7 program through Project 618082 ACMOL and NWO through a VENI fellowship.

We use the electrode-less time-resolved microwave conductivity (TRMC) technique to characterize spin-crossover (SCO) nanoparticles. We show that TRMC is a simple and accurate mean for simultaneously as-sessing the magnetic state of SCO compounds and charge transport information on the nanometre length scale. In the low-spin state from liquid nitrogen temperature up to 360 K the TRMC measurements present two well-defined regimes in the mobility and in the half-life times, possessing similar transition tempera-tures TR near 225 K. Below TR, an activation-less regime associated with short lifetimes of the charge carri-ers points at the presence of shallow-trap states. Above TR, these states are thermally released yielding a thermally activated hopping regime where longer hops increases the mobility and, concomitantly, the barrier energy. The activation energy could originate from intricate contributions such as polaronic self-localizations, but also from dynamic disorder due to phonons and/or thermal fluctuations of SCO moieties., Comment: 9 pages, 5 figures, Supplementary Information

We measure the thermal time constants of suspended single layer molybdenum disulfide drums by their thermomechanical response to a high-frequency modulated laser. From this measurement the thermal diffusivity of single layer MoS$_2$ is found to be 1.14 $\times$ 10$^{-5}$ m$^2$/s on average. Using a model for the thermal time constants and a model assuming continuum heat transport, we extract thermal conductivities at room temperature between 10 to 40 W/(m$\cdot$K). Significant device-to-device variation in the thermal diffusivity is observed. Based on statistical analysis we conclude that these variations in thermal diffusivity are caused by microscopic defects that have a large impact on phonon scattering, but do not affect the resonance frequency and damping of the membrane's lowest eigenmode. By combining the experimental thermal diffusivity with literature values of the thermal conductivity, a method is presented to determine the specific heat of suspended 2D materials, which is estimated to be 255 $\pm$ 104 J/(kg$\cdot$K) for single layer MoS$_2$.

To realize nanomechanical graphene-based pressure and gas sensors, it is beneficial to have a method to electrically readout the static displacement of a suspended graphene membrane. Capacitive readout, typical in micro-electro-mechanical systems (MEMS), gets increasingly challenging as one starts shrinking the dimensions of these devices, since the expected responsivity of such devices is below 0.1 aF/Pa. To overcome the challenges of detecting small capacitance changes, we design an electrical readout device fabricated on top of an insulating quartz substrate, maximizing the contribution of the suspended membrane to the total capacitance of the device. The capacitance of the drum is further increased by reducing the gap size to 110 nm. Using external pressure load, we demonstrate successful detection of capacitance changes of a single graphene drum down to 50 aF, and pressure differences down to 25 mbar.

Molecular electronics aims at exploiting the internal structure and electronic orbitals of molecules to construct functional building blocks(1). To date, however, the overwhelming majority of experimentally realized single-molecule junctions can be described as single quantum dots, where transport is mainly determined by the alignment of the molecular orbital levels with respect to the Fermi energies of the electrodes(2) and the electronic coupling with those electrodes(3,4). Particularly appealing exceptions include molecules in which two moieties are twisted with respect to each others(5,6) and molecules in which quantum interference effects are possible(7,8). Here, we report the experimental observation of pronounced negative differential conductance in the current-voltage characteristics of a single molecule in break junctions. The molecule of interest consists of two conjugated arms, connected by a non-conjugated segment, resulting in two coupled sites. A voltage applied across the molecule pulls the energy of the sites apart, suppressing resonant transport through the molecule and causing the current to decrease. A generic theoretical model based on a two-site molecular orbital structure captures the experimental findings well, as confirmed by density functional theory with non-equilibrium Green's functions calculations that include the effect of the bias. Our results point towards a conductance mechanism mediated by the intrinsic molecular orbitals alignment of the molecule.

Hydrogen and oxygen surface-terminated nanocrystalline diamond (NCD) films are studied by the contactless time-resolved microwave conductivity (TRMC) technique and X-ray photoelectron spectroscopy (XPS). The optoelectronic properties of undoped NCD films are strongly affected by the type of surface termination. Upon changing the surface termination from oxygen to hydrogen, the TRMC signal rises dramatically. For an estimated quantum yield of 1 for sub-bandgap optical excitation the hole mobility of the hydrogen-terminated undoped NCD was found to be ∼0.27 cm(2)/(V s) with a lifetime exceeding 1 μs. Assuming a similar mobility for the oxygen-terminated undoped NCD a lifetime of ∼100 ps was derived. Analysis of the valence band spectra obtained by XPS suggests that upon oxidation of undoped NCD the surface Fermi level shifts (toward an increased work function). This shift originates from the size and direction of the electronic dipole moment of the surface atoms, and leads to different types of band bending at the diamond/air interface in the presence of a water film. In the case of boron-doped NCD no shift of the work function is observed, which can be rationalized by pinning of the Fermi level. This is confirmed by TRMC results of boron-doped NCD, which show no dependency on the surface termination. We suggest that photoexcited electrons in boron-doped NCD occupy nonionized boron dopants, leaving relatively long-lived mobile holes in the valence band.

The isolation of graphene and transition metal dichalcongenides has opened a veritable world to a great number of layered materials which can be exfoliated, manipulated, and stacked or combined at will. With continued explorations expanding to include other layered materials with unique attributes, it is becoming clear that no one material will fill all the post-silicon era requirements. Here we review the properties and applications of layered, quasi-1D transition metal trichalcogenides (TMTCs) as novel materials for next generation electronics and optoelectronics. The TMTCs present a unique chain-like structure which gives the materials their quasi-1D properties such as high anisotropy ratios in conductivity and linear dichroism. The range of band gaps spanned by this class of materials (0.2 eV-2 eV) makes them suitable for a wide variety of applications including field-effect transistors, infrared, visible and ultraviolet photodetectors, and unique applications related to their anisotropic properties which opens another degree of freedom in the development of next generation electronics. In this review we survey the historical development of these remarkable materials with an emphasis on the recent activity generated by the isolation and characterization of atomically thin titanium trisulfide (TiS3)., This work was supported by the Netherlands Organization for Scientific Research (NWO/FOM). AJM-M acknowledges the financial support of MINISTERIO DE CIENCIA E INNOVACIÓN (MICINN) (Spain) through the scholarship BES2012–057346. R.D’A and RB acknowledge financial support by the DYN-XC-TRANS (Grant No. FIS2013-43130-P), NanoTHERM (Grant No. CSD2010- 00044), and SElecT-DFT (FIS2016-79464-P) of the Ministerio de Economia y Competitividad (MINECO), and Grupo Consolidado UPV/EHU del Gobierno Basco (Grant No. IT578-13). RB acknowledges the financial support of the Ministerio de Educacion, Cultura y Deporte (Grant No. FPU12/01576). AC-G acknowledges financial support from the European Commission under the Graphene Flagship, contract CNECTICT-604391, from the MINECO (Ramón y Cajal 2014 program, RYC-2014-01406) and from the MICINN (MAT2014-58399-JIN). MIRE Group thanks MINECO (MAT2015-65203R) for financial support. E Flores also acknowledges the Mexican National Council for Science and Technology (CONACyT).

Previous statistical studies on the mechanical properties of chemical-vapor-deposited (CVD) suspended graphene membranes have been performed by means of measuring individual devices or with techniques that affect the material. Here, we present a colorimetry technique as a parallel, non-invasive, and affordable way of characterizing suspended graphene devices. We exploit Newton rings interference patterns to study the deformation of a double-layer graphene drum 13.2 micrometer in diameter when a pressure step is applied. By studying the time evolution of the deformation, we find that filling the drum cavity with air is 2-5 times slower than when it is purged.

We investigate transport through mechanically triggered single-molecule switches that are based on the coordination sphere-dependent spin state of Fe(II)-species. In these molecules, in certain junction configurations the relative arrangement of two terpyridine ligands within homoleptic Fe(II)-complexes can be mechanically controlled. Mechanical pulling may thus distort the Fe(II) coordination sphere and eventually modify their spin state. Using the movable nanoelectrodes in a mechanically controlled break-junction at low temperature, current-voltage measurements at cryogenic temperatures support the hypothesized switching mechanism based on the spin-crossover behavior. A large fraction of molecular junctions formed with the spin-crossover-active Fe(II)-complex displays a conductance increase for increasing electrode separation and this increase can reach 1-2 orders of magnitude. Theoretical calculations predict a stretching-induced spin transition in the Fe(II)-complex and a larger transmission for the high-spin configuration.

In the pursuit of down-sizing electronic components, the ultimate limit is the use of single molecules as functional devices. The first theoretical proposal of such a device, predicted more than four decades ago, is the seminal Aviram–Ratner rectifier that exploits the orbital structure of the molecule. The experimental realization of single-molecule rectifiers, however, has proven to be challenging. In this work, we report on the experimental realization of a gate-tunable single-molecule rectifier with rectification ratios as high as 600. The rectification mechanism arises from the molecular structure and relies on the presence of two conjugated sites that are weakly coupled through a saturated linker. The observed gate dependence not only demonstrates tunability of the rectification ratio, it also shows that the proposed rectification mechanism based on the orbital structure is operative in the molecule.

Thin layers of black phosphorus present an ideal combination of a 2D material with a tunable direct bandgap and high carrier mobility. However the material suffers from degradation in ambient conditions due to an oxidation reaction which involves water, oxygen and light. We have measured the spatial profile of the conductivity on flakes of black phosphorus as a function of time using scanning microwave impedance microscopy. A microwave excitation (3 GHz) allows to image a conducting sample even when covered with a dielectric layer. We observe that on bare black phosphorus, the conductivity changes drastically over the whole surface within a day. We demonstrate that the degradation process is slowed down considerably by covering the material with a 10 nm layer of hafnium oxide. It is stable for more than a week, opening up a route towards stable black phosphorus devices in which the high dielectric constant of hafnium oxide can be exploited. Covering black phosphorus with a 15 nm boron nitride flake changes the degradation process qualitatively, it is dominated by the edges of the flake indicating a diffusive process and happens on the scale of days., Accepted for publication in 2D Materials

Membranes of suspended two-dimensional materials show a large variability in mechanical properties, in part due to static and dynamic wrinkles. As a consequence, experiments typically show a multitude of nanomechanical resonance peaks, which makes an unambiguous identification of the vibrational modes difficult. Here, we probe the motion of graphene nanodrum resonators with spatial resolution using a phase-sensitive interferometer. By simultaneously visualizing the local phase and amplitude of the driven motion, we show that unexplained spectral features represent split degenerate modes. When taking these into account, the resonance frequencies up to the eighth vibrational mode agree with theory. The corresponding displacement profiles however, are remarkably different from theory, as small imperfections increasingly deform the nodal lines for the higher modes. The Brownian motion, which is used to calibrate the local displacement, exhibits a similar mode pattern. The experiments clarify the complicated dynamic behaviour of suspended two-dimensional materials, which is crucial for reproducible fabrication and applications.

Graphene electrodes are promising candidates to improve reproducibility and stability in molecular electronics through new electrode-molecule anchoring strategies. Here we report sequential electron transport in few-layer graphene transistors containing individual curcuminoid-based molecules anchored to the electrodes via pi-pi orbital bonding. We show the coexistence of inelastic co-tunneling excitations with single-electron transport physics owing to an intermediate molecule-electrode coupling; we argue that an intermediate electron-phonon coupling is the origin of these vibrational-assisted excitations. These experimental observations are complemented with density functional theory calculations to model electron transport and the interaction between electrons and vibrational modes of the curcuminoid molecule. We find that the calculated vibrational modes of the molecule are in agreement with the experimentally observed excitations.

We present graphene quantum dots endowed with addition energies as large as 1.6 eV, fabricated by the controlled rupture of a graphene sheet subjected to a large electron current in air. The size of the quantum dot islands is estimated to be in the 1 nm range. The large addition energies allow for Coulomb blockade at room temperature, with possible application to single-electron devices.

Cruciform motifs with two orthogonally oriented π-extended tetrathiafulvalenes and with differently protected thiolate end-groups are synthesized by stepwise coupling reactions. The molecules are subjected to single-molecule conductivity studies in a break-junction and to conducting probe atomic force microscopy studies in a self-assembled monolayer on gold.