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Nanoscale heat transport is of increasing importance as it often defines performance of modern processors and thermoelectric nanomaterials, and affects functioning of chemical sensors and biosensors. Scanning thermal microscopy (SThM) is the leading tool for nanoscale mapping of thermal properties, but it is often negatively affected by unstable tip–surface thermal contacts. While operating SThM in-liquid environment may allow unimpeded thermal contact and open new application areas, it has so far been regarded as impossible due to increased heat dissipation into the liquid, and the perceived reduced spatial thermal resolution. Nevertheless, in this paper we show that such liquid immersion SThM (iSThM) is fully feasible and, while its thermal sensitivity and spatial resolution is somewhat below that of in-air SThM, it has sufficient thermal contrast to detect thermal conductivity variations in few tens of nm thick graphite nanoflake and metal–polymer nanostructured interconnects. Our results confirm that thermal sensing in iSThM can provide nanoscale resolution on the order of 30 nm, that, coupled with the absence of tip snap-in due to the elimination of capillary forces, opens the possibility for nanoscale thermal mapping in liquids, including thermal phenomena in energy storage devices, catalysts and biosystems. [ABSTRACT FROM AUTHOR]

Bismuth(III) sulfide (Bi 2 S 3) is a promising cathode material for aqueous zinc ion batteries (ZIBs), yet suffers from serious capacity issues due to its poor electrical conductivity and microstructural degradations. In this work, Bi 2 S 3 anchored on reduced graphene oxide (rGO) is prepared through hydrothermal reaction and is used as cathode material for aqueous ZIBs. Raman and XPS characterizations confirmed that the oxygen bridge in Bi–O–C heterostructures is successfully created during the hydrothermal synthesis. These oxygen bridges are energy favourable in the Bi 2 S 3 /rGO composite materials and serve as the electron transfer channels for rapid charge compensation during Zn2+ incorporation/extraction. Rotating ring–disc electrode (RRDE) measurements demonstrate improved electrochemical stability of the Bi 2 S 3 /rGO composite material compared to pristine Bi 2 S 3. As a result of these improved characteristics, Bi 2 S 3 /rGO composite shows notably better rate performance and cycling stability than unsupported Bi 2 S 3. Ex-situ X-ray diffraction and XPS characterizations indicate that Zn2+ undergoes a reversible conversion reaction with Bi 2 S 3 to form ZnS/Bi0, rather than being intercalated into Bi 2 S 3 crystal interlayers. The rGO substrate forms chemical bonds with bismuth in the composite material, and the strongly anchored bismuth on the rGO through a Bi–O–C bridge enables a highly reversible conversion reaction. As a result, the Bi 2 S 3 /rGO composite with 8 wt% rGO can deliver a reversible capacity of ∼186 mAh g−1 at the current density of 500 mA g−1 after 150 cycles, showing high promise as Zn-ion battery material. [ABSTRACT FROM AUTHOR]

All-solid-state Li-metal batteries (ASSLBs) are highly desirable, due to their inherent safety and high energy density; however, the irregular and uncontrolled growth of Li filaments is detrimental to interfacial stability and safety. Herein, we report on the incorporation of piezo-/ferroelectric BaTiO3 (BTO) nanofibers into solid electrolytes and determination of electric-field distribution due to BTO inclusion that effectively regulates the nucleation and growth of Li dendrites. Theoretical simulations predict that the piezoelectric effect of BTO embedded in solid electrolyte reduces the driving force of dendrite growth at high curvatures, while its ferroelectricity reduces the overpotential, which helps to regularize Li deposition and Li+ flux. Polarization reversal of soft solid electrolytes was identified, confirming a regular deposition and morphology alteration of Li. As expected, the ASSLBs operating with LiFePO4/Li and poly(ethylene oxide) (PEO)/garnet solid electrolyte containing 10% BTO additive showed a steady and long cycle life with a reversible capacity of 103.2 mAh g-1 over 500 cycles at 1 C. Furthermore, the comparable cyclability and flexibility of the scalable pouch cells prepared and the successful validation in the sulfide electrolytes, demonstrating its universal and promising application for the integration of Li metal anodes in solid-state batteries. [ABSTRACT FROM AUTHOR]

The harmless disposal of lead paste in the spent lead-acid batteries (LABs) remains an enormous challenge in traditional pyrometallurgical recycling. Here, we introduced a hydrometallurgical method for the recycling of the spent LABs' waste to obtain the β -PbO as a novel zinc ion batteries (ZIBs) active material. The obtained β -PbO exhibits ultra-flat charge/discharge voltage platforms (0.21 mV/(mAh g−1)) and stable specific capacity. During the charge/discharge, the β -PbO spontaneously triggers the formation of (ZnSO 4)[Zn(OH) 2 ] 3 ·5H 2 O (ZHS) micro-sheets as a surface passivation layer. Moreover, the ex-situ X-ray spectra reveal that the reversible phase transformation occurs between PbSO 4 and Pb with the assistance of ZHS by adjusting the PH value on the electrode-electrolyte interface. The synergistic two-phase-reaction mechanism generates ultra-flat voltage platforms upon the charge/discharge. This "energy-saving and environment-friendly" recycling route eliminates the major source of emission of pollution particulates/gases compared to the traditional pyrometallurgical recycling, while at the same time replacing energy-consuming and environmentally detrimental processes of synthesis of current ZIBs cathodes. [ABSTRACT FROM AUTHOR]

While mechanical and frictional propertiesof graphene in air havebeen extensively studied, graphene’s nanomechanical behaviorin liquids, vital for its operation in rechargeable batteries, supercapacitors,and sensors, is still largely unexplored. In this paper, we investigatethe nanomechanics of normal (adhesive and elastic) and tangential(friction) forces between a stationary, moving, and ultrasonicallyexcited nanoscale atomic force microscope (AFM) tip and exfoliatedfew layer graphene (FLG) on SiO2substrate as a functionof surrounding mediaair, polar (water), and nonpolar (dodecane)liquids. We find that, while the friction coefficient is significantlyreduced in liquids, and is always lower for FLG than SiO2, it is higher for graphene in nonpolar dodecane than highly polarwater. We also confirm that in ambient environment the water meniscusdominates high adhesion for both hydrophobic FLG and the more hydrophilicSiO2surface, with the lowest adhesion observed in liquids,in particular for FLG in dodecane, reflecting the low interface energyof this system. By using nanomechanical probing via ultrasonic forcemicroscopy (UFM), we observed a profound reduction of graphene ripplingand increase of graphene–substrate contact area in liquid environment.Friction force dependence on ultrasonic modulation amplitude suggeststhat dodecane at the graphene interface produces a solid-like “cushion”of approximately 2 nm thickness, whereas, in water immersion, thesame dependence shows a remarkable similarity with the ambient environment,confirming the presence of a water meniscus in air, and suggestingnegligible thickness of a similar water “cushion” ongraphene. Dependence of friction on local environment opens new pathwaysfor friction management in microfluidic and micro- and nanoelectromechanicalsystems. [ABSTRACT FROM AUTHOR]

Abstract: The analysis of the formation of ultra-thin organic films is a very important issue. In fact, it is known that the properties of organic light emitting diodes and field effect transistors are strongly affected by the early growth stages. For instance, in the case of sexithiophene, the presence of domains made of molecules with the backbone parallel to the substrate surface has been indirectly evidenced by photoluminescence spectroscopy and confocal microscopy. On the contrary, conventional scanning force microscopy both in contact and intermittent contact modes have failed to detect such domains. In this paper, we show that Ultrasonic Force Microscopy (UFM), sensitive to nanomechanical properties, allows one to directly identify the structure of sub-monolayer thick films. Sexithiophene flat domains have been imaged for the first time with nanometer scale spatial resolution. A comparison with lateral force and intermittent contact modes has been carried out in order to explain the origins of the UFM contrast and its advantages. In particular, it indicates that UFM is highly suitable for investigations where high sensitivity to material properties, low specimen damage and high spatial resolution are required. [Copyright &y& Elsevier]

Understanding the fundamentals of surface decoration effects in phase‐separation materials, such as lithium titanate (LTO), is important for optimizing the lithium‐ion battery (LIB) performance. LTO polycrystalline thin‐film electrodes with and without doped Al–ZnO (AZO) surface coating decoration are used as ideal models to gain insights into the mechanisms involved. Operando shear force modulation spectroscopy is used to observe for the first time the nanoscale dynamics of solid‐electrolyte‐interphase (SEI) formation on the electrode surfaces, confirming that the AZO coating is electrochemically converted into a stiff, homogenous SEI layer that protects the surface from the electrolyte‐induced decomposition. This AZO layer and its resultant artificial SEI‐layer have higher Li‐ion transport rates than the unmodified surface. These layers can reduce barriers to surface nucleation and facilitate rapid redistribution of lithium‐ions during the Li4Ti5O12 ⇄ Li7Ti5O12 phase separation, significantly inhabiting the orderly collective phase‐separation behavior (electrochemical oscillation) in the LTO electrode. The suppressed voltage oscillations indicate more homogeneous local exchange current density and de/intercalation states with the decorated electrodes, thereby extending their battery efficiency and long‐term cycling stability. This work highlights the ultimate importance of surface treatment for LIB materials for determining their interfacial chemistry and phase transition during the intercalation/deintercalation. [ABSTRACT FROM AUTHOR]

Induced disorder in graphene enables changes in electrical and thermal transport. It has been shown previously that disorder is very important for electron cooling in graphene through disorder-assisted electron-phonon scattering, particularly via the supercollisions process. Here we study electron-momentum relaxation due to electron-phonon scattering while increasing the degree of disorder. With in-situ scanning thermal microscopy we monitor the temperature rise in the constriction region of a bowtie-shaped graphene device while increasing the disorder by means of feedback-controlled voltage ramps at high-current densities. Analysis of the combined thermal and electrical measurements in the low bias regime shows that the relative change of the momentum scattering rate vs temperature, as measured at room temperature, increases with strong local disorder. By excluding other candidate mechanisms for this phenomenon, including a change of the charge carriers density and activation of optical phonons, we conclude that the increase we observe in the temperature-dependent component of the scattering rate is likely due to new acoustic phonon scattering channels that open up as disorder increases. [Display omitted] [ABSTRACT FROM AUTHOR]

The open circuit voltage (VOC) is a critical and common indicator of solar cell performance as well as degradation, for panel down to lab-scale photovoltaics. Detecting VOC at the nanoscale is much more challenging, however, due to experimental limitations on spatial resolution, voltage resolution, and/or measurement times. Accordingly, an approach based on Conductive Atomic Force Microscopy is implemented to directly detect the local VOC, notably for monocrystalline Passivated Emitter Rear Contact (PERC) cells which are the most common industrial-scale solar panel technology in production worldwide. This is demonstrated with cross-sectioned monocrystalline PERC cells around the entire circumference of a poly-aluminum-silicide via through the rear emitter. The VOC maps reveal a local back surface field extending ~ 2 μm into the underlying p-type Si absorber due to Al in-diffusion as designed. Such high spatial resolution methods for photovoltaic performance mapping are especially promising for directly visualizing the effects of processing parameters, as well as identifying signatures of degradation for silicon and other solar cell technologies. [ABSTRACT FROM AUTHOR]

Biomaterials capable of controlling the delivery of drugs have the potential to treat a variety of conditions. Herein, the preparation of electrically conductive silk fibroin film‐based drug delivery devices is described. Casting aqueous solutions of Bombyx mori silk fibroin, followed by drying and annealing to impart β‐sheets to the silk fibroin, assure that the materials are stable for further processing in water; and the silk fibroin films are rendered conductive by generating an interpenetrating network of a copolymer of pyrrole and 3‐amino‐4‐hydroxybenzenesulfonic acid in the silk fibroin matrix (characterized by a variety of techniques including circular dichroism, Fourier‐transform infrared spectroscopy, nuclear magnetic resonance, Raman spectroscopy, resistance measurements, scanning electron microscopy‐energy dispersive X‐ray spectroscopy, thermogravimetric analysis, X‐ray diffraction, and X‐ray photoelectron spectroscopy). Fibroblasts adhere on the surface of the biomaterials (viability assessed using an (3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide) assay and visualized using a confocal microscope), and a fluorescently labeled drug (Texas‐Red Gentamicin) can be loaded electrochemically and released (µg cm−2 quantities) in response to the application of an electrical stimulus. [ABSTRACT FROM AUTHOR]

A true non-intrusive 3D Micro-Acoustic Trap for a controlled monolayer assembly of microparticles in aqueous environment. Modulation of acoustic pressure generated by an acoustic lens can assist in particle manipulation and formation of a monolayer of polystyrene beads suspended in aqueous media. The same experimental model can also be used for manipulating and probing live cells. • Micro-Acoustic Trap for controlled assembly of microparticles as a monolayer suspended in aqueous media. • A suspended 2D monolayer of polystyrene beads with hexagonal close pack lattice with high density of particles. • Multilayered monolayer arrangement of microparticles in 3D. • Acoustically controlled mobility and segregation of live cell. Acoustic tweezers facilitate the manipulation of objects using sound waves. With the current state of the technology one can only control mobility for a single or few microparticles. This article presents a state of the art system where an Acoustic Lens was used for developing a Micro-Acoustic Trap for microparticle assembly in 3D. The model particles, 2 µm diameter polystyrene beads in suspension, were driven via acoustic pressure to form a monolayer at wavelength-defined distances above the substrate defined by the focal point of an Acoustic Lens The transducer was driven at 89 MHz, mixed with 100 ms pulses at a repetition rate of 2 Hz. Beyond a threshold drive amplitude sufficient to overcome Brownian motion, this led to 2D assembly of the microparticles into close-packed rafts >80 µm across (∼5 wavelengths of the carrier wave and >40 particles across). This methodology was further extended to manipulation of live Dictyostelium discoideum amoebae. This approach therefore offers maneuverability in controlling or assembling micrometer-scale objects using continuous or pulsed focused acoustic radiation pressure. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Although it was demonstrated that discrete molecular levels determine the sign and magnitude of the thermoelectric effect in single-molecule junctions, full electrostatic control of these levels has not been achieved to date. Here, we show that graphene nanogaps combined with gold microheaters serve as a testbed for studying single-molecule thermoelectricity. Reduced screening of the gate electric field compared to conventional metal electrodes allows control of the position of the dominant transport orbital by hundreds of meV. We find that the power factor of graphene-fullerene junctions can be tuned over several orders of magnitude to a value close to the theoretical limit of an isolated Breit-Wigner resonance. Furthermore, our data suggest that the power factor of an isolated level is only given by the tunnel coupling to the leads and temperature. These results open up new avenues for exploring thermoelectricity and charge transport in individual molecules and highlight the importance of level alignment and coupling to the electrodes for optimum energy conversion in organic thermoelectric materials. [ABSTRACT FROM AUTHOR]

Scanning thermal microscopy (SThM), which enables measurement of thermal transport and temperature distribution in devices and materials with nanoscale resolution is rapidly becoming a key approach in resolving heat dissipation problems in modern processors and assisting development of new thermoelectric materials. In SThM, the self-heating thermal sensor contacts the sample allowing studying of the temperature distribution and heat transport in nanoscaled materials and devices. The main factors that limit the resolution and sensitivities of SThM measurements are the low efficiency of thermal coupling and the lateral dimensions of the probed area of the surface studied. The thermal conductivity of the sample plays a key role in the sensitivity of SThM measurements. During the SThM measurements of the areas with higher thermal conductivity the heat flux via SThM probe is increased compared to the areas with lower thermal conductivity. For optimal SThM measurements of interfaces between low and high thermal conductivity materials, well defined nanoscale probes with high thermal conductivity at the probe apex are required to achieve a higher quality of the probe-sample thermal contact while preserving the lateral resolution of the system. In this paper, we consider a SThM approach that can help address these complex problems by using high thermal conductivity nanowires (NW) attached to a tip apex. We propose analytical models of such NW-SThM probes and analyse the influence of the contact resistance between the SThM probe and the sample studied. The latter becomes particularly important when both tip and sample surface have high thermal conductivities. These models were complemented by finite element analysis simulations and experimental tests using prototype probe where a multiwall carbon nanotube (MWCNT) is exploited as an excellent example of a high thermal conductivity NW. These results elucidate critical relationships between the performance of the SThM probe on one hand and thermal conductivity, geometry of the probe and its components on the other. As such, they provide a pathway for optimizing current SThM for nanothermal studies of high thermal conductivity materials. Comparison between experimental and modeling results allows us to provide direct estimates of the contact thermal resistances for various interfaces such as MWCNT-Al (5×10 −9 ±1×10 −9 K m 2 W −1 ), Si 3 N 4 –Al (6×10 −8 ±2.5×10 −8 K m 2 W −1 ) and Si 3 N 4 −graphene (~10 −8 K m 2 W −1 ). It was also demonstrated that the contact between the MWCNT probe and Al is relatively perfect, with a minimal contact resistance. In contrast, the thermal resistance between a standard Si 3 N 4 SThM probe and Al is an order of magnitude higher than reported in the literature, suggesting that the contact between these materials may have a multi-asperity nature that can significantly degrade the contact resistance. [ABSTRACT FROM AUTHOR]

Nanosecond scale threshold switching is investigated with conducting atomic force microscopy (AFM) for an amorphous GeSe film. Switched bits exhibit 2-3 orders of magnitude variations in conductivity, as demonstrated in phase change based memory devices. Through the nm-scale AFM probe, this crystallization was achieved with pulse durations of as low as 15 ns, the fastest reported with scanning probe based methods. Conductance AFM imaging of the switched bits further reveals correlations between the switched volume, pulse amplitude, and pulse duration. The influence of film heterogeneities on switching is also directly detected, which is of tremendous importance for optimal device performance. [ABSTRACT FROM AUTHOR]

We report direct imaging of nanoscale thermal transportin singleand few-layer graphene with approximately 50 nm lateral resolutionusing high vacuum scanning thermal microscopy. We observed increasedheat transport in suspended graphene where heat is conducted by ballisticphonons, compared to adjacent areas of supported graphene, and observeddecreasing thermal conductance of supported graphene with increasedlayer number. Our nanothermal images suggest a mean-free-path of thermalphonons in supported graphene below 100 nm. [ABSTRACT FROM AUTHOR]

In this paper, we present a study of tungsten disulfide (WS2) two-dimensional (2D) crystals, grown on epitaxial Graphene. In particular, we have employed scanning electron microscopy (SEM) and µRaman spectroscopy combined with multifunctional scanning probe microscopy (SPM), operating in peak force–quantitative nano mechanical (PF-QNM), ultrasonic force microscopy (UFM) and electrostatic force microscopy (EFM) modes. This comparative approach provides a wealth of useful complementary information and allows one to cross-analyze on the nanoscale the morphological, mechanical, and electrostatic properties of the 2D heterostructures analyzed. Herein, we show that PF-QNM can accurately map surface properties, such as morphology and adhesion, and that UFM is exceptionally sensitive to a broader range of elastic properties, helping to uncover subsurface features located at the buried interfaces. All these data can be correlated with the local electrostatic properties obtained via EFM mapping of the surface potential, through the cantilever response at the first harmonic, and the dielectric permittivity, through the cantilever response at the second harmonic. In conclusion, we show that combining multi-parametric SPM with SEM and µRaman spectroscopy helps to identify single features of the WS2/Graphene/SiC heterostructures analyzed, demonstrating that this is a powerful tool-set for the investigation of 2D materials stacks, a building block for new advanced nano-devices. [ABSTRACT FROM AUTHOR]