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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

Creating a good contact between electrodes and graphene nanoribbons (GNRs) has been a long-standing challenge in searching for the next GNR-based nanoelectronics. This quest requires the controlled fabrication of sub-20 nm metallic gaps, a clean GNR transfer minimizing damage and organic contamination during the device fabrication, as well as work function matching to minimize the contact resistance. Here, we transfer 9-atom-wide armchair-edged GNRs (9-AGNRs) grown on Au(111)/mica substrates to pre-patterned platinum electrodes, yielding polymer-free 9-AGNR field-effect transistor devices. Our devices have a resistance in the range of 106-108 Ω in the low-bias regime, which is 2-4 orders of magnitude lower than previous reports. Density functional theory calculations combined with the non-equilibrium Green's function method explain the observed p-type electrical characteristics and further demonstrate that platinum gives strong coupling and higher transmission in comparison to other materials, such as graphene., Applied Physics Letters, 122 (17), ISSN:0003-6951, ISSN:1077-3118

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

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

Probing the universal low temperature magnetic field scaling of Kondo-correlated quantum dots via electrical conductance has proved to be experimentally challenging. Here, we show how to probe this in nonlinear thermocurrent spectroscopy applied to a molecular quantum dot in the Kondo regime. Our results demonstrate that the bias-dependent thermocurrent is a sensitive probe of universal Kondo physics, directly measures the splitting of the Kondo resonance in a magnetic field, and opens up possibilities for investigating nanosystems far from thermal and electrical equilibrium., Comment: Published version, including Supplementary Material main text:6 pages, 4 figures. SI: 55 pages, 22 figures

The charge density wave (CDW) state in van der Waals systems shows interesting scaling phenomena as the number of layers can significantly affect the CDW transition temperature, $T_{CDW}$. However, it is often difficult to use conventional methods to study the phase transition in these systems due to their small size and sensitivity to degradation. Degradation is an important parameter which has been shown to greatly influence the superconductivity in layered systems. Since the CDW state competes with the onset of superconductivity, it is expected that $T_{CDW}$ will also be affected by the degradation. Here, we probe the CDW phase transition by the mechanical resonances of suspended 2H-TaS2 and 2H-TaSe2 membranes and study the effect of disorder on the CDW state. Pristine flakes show the transition near the reported values of 75 K and 122 K respectively. We then study the effect of degradation on 2H-TaS2 which displays an enhancement of $T_{CDW}$ up to 129 K after degradation in ambient air. Finally, we study a sample with local degradation and observe that multiple phase transitions occur at 87 K, 103 K and 118 K with a hysteresis in temperature in the same membrane. The observed spatial variations in the Raman spectra suggest that variations in crystal structure cause domains with different transition temperatures which could result in the hysteresis. This work shows the potential of using nanomechanical resonance to characterize the CDW in suspended 2D materials and demonstrate that degradation can have a large effect on transition temperatures., The following article has been accepted by Applied Physics Letters. After it is published, it will be found at [https://doi.org/10.1063/5.0051112]

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

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.

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 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.

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

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

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

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

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

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.

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.

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.

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.

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

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

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.

Bejarano, Francesc et al., Organic paramagnetic and electroactive molecules are attracting interest as core components of molecular electronic and spintronic devices. Currently, further progress is hindered by the modest stability and reproducibility of the molecule/electrode contact. We report the synthesis of a persistent organic radical bearing one and two terminal alkyne groups to form Au-C σ bonds. The formation and stability of self-assembled monolayers and the electron transport through single-molecule junctions at room temperature have been studied. The combined analysis of both systems demonstrates that this linker forms a robust covalent bond with gold and a better-defined contact when compared to traditional sulfur-based linkers. Density functional theory and quantum transport calculations support the experimental observation highlighting a reduced variability of conductance values for the C-Au based junction. Our findings advance the quest for robustness and reproducibility of devices based on electroactive molecules., We acknowledge Dr. G. Sauthier from the ICN2 for the XPS measurements, Prof. Carlos Gomez from IcMOL for the SQUID measurements, A. Bernabé and Dr. V. Lloveras from ICMAB for the LDI-ToF and EPR measurements, respectively. This work was supported by FET ACMOL project (GA no. 618082), CIBER-BBN, the DGI (Spain) project FANCY CTQ2016-80030-R, the Generalitat de Catalunya (2014-SGR-17) and the MINECO, through the “Severo Ochoa” Programme for Centers of Excel-lence in R&D (SEV-2015-0496). F.B he is enrolled in the Materi-als Science Ph.D. program of UAB. We thank the Dutch science foundation NWO/FOM for financial support.

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).

Graphene, the carbon monolayer and 2D allotrope of graphite, has the potential to impact technology with a wide range of applications such as optical modulators for high-speed communications. In contrast to modulation devices that rely on plasmonic or electronic effects, MEMS-based modulators can have wider tuning ranges albeit at a lower operating frequency. These properties make electro-optic mechanical modulators ideal for reflective-type display technologies as has been demonstrated previously with SiN membranes in Interferometric MOdulator Displays (IMODs). Despite their low-power consumption and performance in bright environments, IMODs suffer from low frame rates and limited color gamut. Double-layer graphene (DLG) membranes grown by chemical vapor deposition (CVD) can also recreate the interference effect like in IMODs as proven with drumheads displaying Newton's rings. Here, we report on the electro-optical response of CVD DLG mechanical pixels by measuring the change in wavelength-dependent reflectance of a suspended graphene drumhead as a function of electrical gating. We use a spectrometer to measure the wavelength spectrum at different voltages, and find a good agreement with a model based on light interference. Moreover, to verify that gas compression effects do not play an important role, we use a stroboscopic illumination technique to study the electro-optic response of these graphene pixels at frequencies up to 400 Hz. Based on these findings, we demonstrate a continuous full-spectrum reflective-type pixel technology with a Graphene Interferometric MOdulator Display (GIMOD) prototype of 2500 pixels per inch (ppi) equivalent to more than 12K resolution., Comment: 13 pages, 4 figures

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.

Island, Joshua O. et al., Superconductors containing magnetic impurities exhibit intriguing phenomena derived from the competition between Cooper pairing and Kondo screening. At the heart of this competition are the Yu-Shiba-Rusinov (Shiba) states which arise from the pair breaking effects a magnetic impurity has on a superconducting host. Hybrid superconductor-molecular junctions offer unique access to these states but the added complexity in fabricating such devices has kept their exploration to a minimum. Here, we report on the successful integration of a model spin 1 / 2 impurity, in the form of a neutral and stable all organic radical molecule, in proximity-induced superconducting break junctions. Our measurements reveal excitations which are characteristic of a spin-induced Shiba state due to the radical’s unpaired spin strongly coupled to a superconductor. By virtue of a variable molecule-electrode coupling, we access both the singlet and doublet ground states of the hybrid system which give rise to the doublet and singlet Shiba excited states, respectively. Our results show that Shiba states are a robust feature of the interaction between a paramagnetic impurity and a proximity-induced superconductor where the excited state is mediated by correlated electron-hole (Andreev) pairs instead of Cooper pairs., The authors thank Jens Paaske for insightful discussions. The authors acknowledge financial support by the Dutch Organization for Fundamental research (FOM), the Ministry of Education, Culture, and Science (OCW), the Netherlands Organization for Scientific Research (NWO), and an ERC advanced grant (MolS@MolS). C. F., M.M.-T., C. R., and J. V. acknowledge the financial support from Spanish Ministry of Economy and Competitiveness, through the DGI (CTQ2013-40480-R) and Severo Ochoa Programme for Centres of Excellence in R&D (SEV-2015-0496), the Generalitat de Catalunya (2014SGR-17) and the Networking Research Center of Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN). T.M. K. acknowledges the support from the European Research Council Advanced Grant No. 339306 (METIQUM) and from the Ministry of Education and Science of the Russian Federation, Contract No. 14.B25.31.0007. R. A. acknowledges Grants No. FIS2012-33521 and No. FIS-2015-64654 (MINECO/FEDER).

The fabrication of van der Waals heterostructures, artificial materials assembled by individual stacking of 2D layers, is among the most promising directions in 2D materials research. Until now, the most widespread approach to stack 2D layers relies on deterministic placement methods, which are cumbersome and tend to suffer from poor control over the lattice orientations and the presence of unwanted interlayer adsorbates. Here, we present a different approach to fabricate ultrathin heterostructures by exfoliation of bulk franckeite which is a naturally occurring and air stable van der Waals heterostructure (composed of alternating SnS 2-like and PbS-like layers stacked on top of each other). Presenting both an attractive narrow bandgap (, A.C.-G. acknowledges financial support from the BBVA Foundation through the fellowship ‘I Convocatoria de Ayudas Fundacion BBVA a Investigadores, Innovadores y Creadores Culturales’ (‘Semiconductores ultradelgados: hacia la optpelectronica flexible’), from the MINECO (Ramón y Cajal 2014 program, RYC-2014-01406), from the MICINN (MAT2014-58399-JIN) and from European Commission under the Graphene Flagship, contract CNECTICT-604391. E.M.P. acknowledges financial support from the European Research Council (MINT, ERC-StG-307609) and from the MINECO of Spain (CTQ2014-60541-P). E.G. gratefully acknowledges the AMAROUT II fellowship program for receiving a grant for transnational mobility (Marie Curie Action, FP7-PEOPLE- 2011-COFUND (291803)). A.J.M.-M., G.R.-B. and N.A. acknowledge the support of the MICCINN/MINECO (Spain) through the programmes MAT2014-57915-R, BES-2012-057346 and FIS2011-23488 and Comunidad de Madrid (Spain) through the programme S2013/MIT-3007 (MAD2D). J.O.I. and H.S.J.v.d.Z. acknowledge the support of the Dutch organization for Fundamental Research on Matter (FOM) and by the Ministry of Education, Culture, and Science (OCW). M.A.N. acknowledeges the support of the MICCINN/MINECO (Spain) through the programmes MAT2013-49893-EXP and MAT2014-59315-R. Authors M.A.N., A.J.M.-M. and A.C.-G. acknowledge the support from ALBA Synchrotron for the experiments performed at Circe beamline (BL24-CIRCE) at ALBA Synchrotron with the collaboration of ALBA staff (proposal ID 2015091399). W.S.P. acknowledges CAPES Foundation, Ministry of Education of Brazil, under grant BEX 9476/13-0. W.S.P. and J.J.P. acknowledge MICCINN/MINECO (Spain) for financial support under grant FIS2013-47328-C02-1; the European Union structural funds and the Comunidad de Madrid MAD2D-CM programme under grant nos. P2013/MIT-3007 and P2013/MIT-2850; the Generalitat Valenciana under grant no. PROMETEO/2012/011

et al., Fullerenes have attracted interest for their possible applications in various electronic, biological, and optoelectronic devices. However, for efficient use in such devices, a suitable anchoring group has to be employed that forms well-defined and stable contacts with the electrodes. In this work, we propose a novel fullerene tetramalonate derivate functionalized with trans-1 4,5-diazafluorene anchoring groups. The conductance of single-molecule junctions, investigated in two different setups with the mechanically controlled break junction technique, reveals the formation of molecular junctions at three conductance levels. We attribute the conductance peaks to three binding modes of the anchoring groups to the gold electrodes. Density functional theory calculations confirm the existence of multiple binding configurations and calculated transmission functions are consistent with experimentally determined conductance values., The work at TUDelft was supported by the EU through an advanced ERC grant (Mols@Mols); device fabrication was done at the Kavli Nanolab at Delft. The work at University of Chile was supported by Fondecyt Regular Project 1161775 (M.S. and J.L.M.), Fondecyt Regular Project 1140770, EU RISE (DAFNEOX) project SEP-210165479 (D.D.), and CONICYT/Fondecyt Postdoctoral Project 3150674 (C.G.C.). D.A. thanks CONICYT + PAI ‘Concurso nacional de apoyo al retorno de investigadores/as desde el extranjero, convocatoria 2014 82140014’ for financial support. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). L.E. thanks the National Science Foundation [grant CHE-1408865] and the PREM Program [grant DMR-1205302] as well as the Robert A. Welch Foundation [grant AH-0033] for generous financial support.

Molecular systems can exhibit a complex, chemically tailorable inner structure which allows for targeting of specific mechanical, electronic and optical properties. At the single-molecule level, two major complementary ways to explore these properties are molecular quantum-dot structures and scanning probes. This article outlines comprehensive principles of electron-transport spectroscopy relevant to both these approaches and presents a new, high-resolution experiment on a high-spin single-molecule junction exemplifying these principles. Such spectroscopy plays a key role in further advancing our understanding of molecular and atomic systems, in particular the relaxation of their spin. In this joint experimental and theoretical analysis, particular focus is put on the crossover between resonant regime [single-electron tunneling (SET)] and the off-resonant regime [inelastic electron (co)tunneling (IETS)]. We show that the interplay of these two processes leads to unexpected mirages of resonances not captured by either of the two pictures alone. Although this turns out to be important in a large fraction of the possible regimes of level positions and bias voltages, it has been given little attention in molecular transport studies. Combined with nonequilibrium IETS -- four-electron pump-probe excitations -- these mirages provide crucial information on the relaxation of spin excitations. Our encompassing physical picture is supported by a master-equation approach that goes beyond weak coupling. The present work encourages the development of a broader connection between the fields of molecular quantum-dot and scanning probe spectroscopy., 28 pages, 16 figures. Submitted to "Journal of Chemical Physics"

The thermal response of graphene is expected to be extremely fast due to its low heat capacity and high thermal conductivity. In this work, the thermal response of suspended single-layer graphene membranes is investigated by characterization of their mechanical motion in response to a high-frequency modulated laser. A characteristic delay time $\ensuremath{\tau}$ between the optical intensity and mechanical motion is observed, which is attributed to the time required to raise the temperature of the membrane. We find, however, that the measured time constants are significantly larger than the predicted ones based on values of the specific heat and thermal conductivity. In order to explain the discrepancy between measured and modeled $\ensuremath{\tau}$, a model is proposed that takes a thermal boundary resistance at the edge of the graphene drum into account. The measurements provide a noninvasive way to characterize thermal properties of suspended atomically thin membranes, providing information that can be hard to obtain by other means.

We realize a strongly coupled double quantum dot in a single all-organic molecule by introducing a nonconjugated bridge in between two identical conjugated moieties. Spin-1/2 Kondo and Kondo enhanced low-energy excitations for, respectively, the odd and even electron occupation are observed in off-resonant transport. The ground state in the even occupation can be the singlet or the triplet state varying between samples. This observation suggests that both antiferromagnetic and ferromagnetic interactions between spins are of the same order of magnitude.

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.

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.