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Scanning tunneling microscopy (STM) is used to examine reactions of 1,3-cyclohexadiene with silicon dimers on bare silicon (100) surface. In addition to the intradimer [2+2] and [4+2] reaction products, two different [2+2] conformers are identified.

The chemisorption of a series of diatomic molecules on the Si(100) surface was studied through scanning tunneling microscopy (STM). Dissociative chemisorption was found to occur and the adatoms produced were observed at two kinds of surface sites. The stability of these sites was examined by exciting the adsorbate system through a tip voltage pulse. The excitation caused the adatoms to undergo a rearrangement that depends both on the nature of the adspecies and on the site being stimulated.

Ge1–xSnx nanowires incorporating a large amount of Sn would be useful for mobility enhancement in nanoelectronic devices, a definitive transition to a direct bandgap for application in optoelectronic devices and to increase the efficiency of the GeSn-based photonic devices. Here we report the catalytic bottom-up fabrication of Ge1–xSnx nanowires with very high Sn incorporation (x > 0.3). These nanowires are grown in supercritical toluene under high pressure (21 MPa). The introduction of high pressure in the vapor–liquid–solid (VLS) like growth regime resulted in a substantial increase of Sn incorporation in the nanowires, with a Sn content ranging between 10 and 35 atom %. The incorporation of Sn in the nanowires was found to be inversely related to nanowire diameter; a high Sn content of 35 atom % was achieved in very thin Ge1–xSnx nanowires with diameters close to 20 nm. Sn was found to be homogeneously distributed throughout the body of the nanowires, without apparent clustering or segregation. The large inclusion of Sn in the nanowires could be attributed to the nanowire growth kinetics and small nanowire diameters, resulting in increased solubility of Sn in Ge at the metastable liquid–solid interface under high pressure. Electrical investigation of the Ge1–xSnx (x = 0.10) nanowires synthesized by the supercritical fluid approach revealed their potential in nanoelectronics and sensor-based applications. [ABSTRACT FROM AUTHOR]

Density functional theory calculations are used to order the predicted frontier wave functions in terms of energy for a single Si dimer unit across the surface Brillouin zone. The calculated frontier states are found to be a valuable tool in describing reactivity on Si(100) that is consistent with experiment and provides a rational means to predict allowed reaction products on Si(100).

The conductive properties of vertically aligned germanium nanowires, with mean diameters of 50 and 100 nm, within anodized aluminum oxide (AAO) templates are characterized by conductive atomic force microscopy (C-AFM) and macrocontact measurements. C-AFM was used to determine the electrical transport properties of individual nanowires within the arrays, while macrocontacts were used to measure the mean current-voltage characteristics of groups of nanowires.

The density functional theory (DFT) is used to study different possible bonding geometries of 1,3-cyclohexadiene (1,3-CHD) on the Si(100)-2x1 surface and to compare these results with the STM experiments. The results obtained are analyzed in terms of the total energy values and the detailed optimized geometries.

Raman spectroscopy is an indispensable tool in the analysis of microplastics smaller than 20 μm. However, due to its limitation, Raman spectroscopy may be incapable of effectively distinguishing microplastics from micro additive particles. To validate this hypothesis, we characterized and compared the Raman spectra of six typical slip additives with polyethylene and found that their hit quality index values (0.93-0.96) are much higher than the accepted threshold value (0.70) used to identify microplastics. To prevent this interference, a new protocol involving an alcohol treatment step was introduced to successfully eliminate additive particles and accurately identify microplastics. Tests using the new protocol showed that three typical plastic products (polyethylene pellets, polyethylene bottle caps, and polypropylene food containers) can simultaneously release microplastic-like additive particles and microplastics regardless of the plastic type, daily-use scenario, or service duration. Micro additive particles can also adsorb onto and modify the surfaces of microplastics in a manner that may potentially increase their health risks. This study not only reveals the hidden problem associated with the substantial interference of additive particles in microplastic detection but also provides a cost-effective method to eliminate this interference and a rigorous basis to quantify the risks associated with microplastic exposure.

Ge 1- x Sn x nanowires incorporating a large amount of Sn would be useful for mobility enhancement in nanoelectronic devices, a definitive transition to a direct bandgap for application in optoelectronic devices and to increase the efficiency of the GeSn-based photonic devices. Here we report the catalytic bottom-up fabrication of Ge 1- x Sn x nanowires with very high Sn incorporation ( x > 0.3). These nanowires are grown in supercritical toluene under high pressure (21 MPa). The introduction of high pressure in the vapor-liquid-solid (VLS) like growth regime resulted in a substantial increase of Sn incorporation in the nanowires, with a Sn content ranging between 10 and 35 atom %. The incorporation of Sn in the nanowires was found to be inversely related to nanowire diameter; a high Sn content of 35 atom % was achieved in very thin Ge 1- x Sn x nanowires with diameters close to 20 nm. Sn was found to be homogeneously distributed throughout the body of the nanowires, without apparent clustering or segregation. The large inclusion of Sn in the nanowires could be attributed to the nanowire growth kinetics and small nanowire diameters, resulting in increased solubility of Sn in Ge at the metastable liquid-solid interface under high pressure. Electrical investigation of the Ge 1- x Sn x ( x = 0.10) nanowires synthesized by the supercritical fluid approach revealed their potential in nanoelectronics and sensor-based applications., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Two-dimensional (2D) layered semiconductors have recently emerged as attractive building blocks for next-generation low-power nonvolatile memories. However, challenges remain in the controllable fabrication of bipolar resistive switching circuit components from these materials. Here, the experimental realization of lateral memtransistors from monolayer single-crystal molybdenum disulfide (MoS 2 ) utilizing a focused helium ion beam is reported. Site-specific irradiation with the focused probe of a helium ion microscope creates a nanometer-scale defect-rich region, bisecting the MoS 2 lattice. The reversible drift of these defects in the applied electric field modulates the resistance of the channel, enabling versatile memristive functionality. The device can reliably retain its resistance ratios and set/reset biases for 1180 switching cycles. Long-term potentiation and depression with sharp habituation are demonstrated. This work establishes the feasibility of ion irradiation for controllable fabrication of 2D memristive devices with promising key performance parameters, such as low power consumption. The applicability of these devices for synaptic emulation may address the demands of future neuromorphic architectures.

Nanoscale materials are frequently coated with surface stabilization layers during growth that prevent flocculation in solution and facilitate processing technologies such as ink-jet device printing. Here, we show that few-nanometer-thick stabilization layers typically used swell in the presence of certain solvents and impart significant stresses to the nanomaterial that remains even after the solvent has evaporated. Solvent swelling of the surface layer dramatically enhances nanomaterial-substrate adhesion via the collapse of the stabilization layer during solvent evaporation, preventing stress relaxation. We demonstrate the stress modulation of Ag, Au, and Si nanowires functionalised with surface polymers and surfactant layers and detect strain levels between 0.1 and 0.6% using atomic force microscopy mechanical measurement and Raman spectroscopy. Dry-transferred nanowires exhibit poor adhesion and show no evidence of incorporated stress but become stressed immediately following solvent exposure. Strain engineering is demonstrated by coating nanowires with few-nanometer-thick solvent-responsive polymer layers.

We combine ambient (air) and ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) and spectroscopy (STS) investigations together with density functional theory (DFT) calculations to gain a subnanometer insight into the structure and dynamic of two-dimensional (2D) surface-supported molecular networks. The planar tetraferrocene-porphyrin molecules employed in this study undergo spontaneous self-assembly via the formation of hydrogen bonded networks at the gold substrate-solution interface. To mimic liquid phase ambient deposition conditions, film formation was accomplished in UHV by electro-spraying a solution of the molecule in chloroform onto an Au(111) substrate, thereby providing access to the full spectroscopic capabilities of STM that can be hardly attained under ambient conditions. We show that molecular assembly on Au (111) is identical in films prepared under the two different conditions, and in good agreement with the theoretical predictions. However, we observe the contrast found for a given STM bias condition to be different in ambient and UHV conditions despite the similarity of the structures, and we propose possible origins of the different imaging contrast. This approach could be valuable for the thorough characterization of surface systems that involve large molecules and are prepared mainly in ambient conditions.

Optically transparent photodetectors are crucial in next-generation optoelectronic applications including smart windows and transparent image sensors. Designing photodetectors with high transparency, photoresponsivity, and robust mechanical flexibility remains a significant challenge, as is managing the inevitable trade-off between high transparency and strong photoresponse. Here we report a scalable method to produce flexible crystalline Si nanostructured wire (NW) networks fabricated from silicon-on-insulator (SOI) with seamless junctions and highly responsive porous Si segments that combine to deliver exceptional performance. These networks show high transparency (∼92% at 550 nm), broadband photodetection (350 to 950 nm) with excellent responsivity (25 A/W), optical response time (0.58 ms), and mechanical flexibility (1000 cycles). Temperature-dependent photocurrent measurements indicate the presence of localized electronic states in the porous Si segments, which play a crucial role in light harvesting and photocarrier generation. The scalable low-cost approach based on SOI has the potential to deliver new classes of flexible optoelectronic devices, including next-generation photodetectors and solar cells.

Nonpolar resistive switching (RS), a combination of bipolar and unipolar RS, is demonstrated for the first time in a single nanowire (NW) system. Exploiting Ag@TiO 2 core-shell (CS) NWs synthesized by postgrowth shell formation, the switching mode is controlled by adjusting the current compliance effectively, tailoring the electrical polarity response. We demonstrate ON/OFF ratios of 10 5 and 10 7 for bipolar and unipolar modes, respectively. In the bipolar regime, retention times could be controlled up to 10 3 s, and in the unipolar mode, >10 6 s was recorded. We show how the unique dual-mode switching behavior is enabled by the defect-rich polycrystalline material structure of the TiO 2 shell and the interaction between the Ag core and the Ag electrodes. These results provide a foundation for engineering nonpolar RS behaviors for memory storage and neuromorphic applications in CSNW structures.

We demonstrate templating of functional materials with unexpected and intricate micro- and nanostructures by controlling the condensation, packing, and evaporation of water droplets on a polymer solution. Spontaneous evaporation of a polymer solution induces cooling of the liquid surface and water microdroplet condensation from the ambient vapor. These droplets pack together and act as a template to imprint an entangled polymer film. This breath figure (BF) phenomenon is an example of self-organization that involves the long-range ordering of droplets. Equilibrium-based analysis provides many insights into contact angles and drop stability of individual drops, but the BF phenomenon remains poorly understood thus far, preventing translation to real applications. Here we investigate the dynamics of this phenomenon to separate out the competing influences and then introduce a modulation scheme to ultimately manipulate the water vapor-liquid equilibrium independently from the solvent evaporation. This approach to BF control provides insights into the mechanism, a rationale for microstructure design, and evidence for the benefits of dynamical control of self-organization systems. We finally present dramatically different porous architectures from this approach reminiscent of microscale Petri dishes, conical flasks, and test tubes.

Networks of silver nanowires appear set to replace expensive indium tin oxide as the transparent conducting electrode material in next generation devices. The success of this approach depends on optimizing the material conductivity, which until now has largely focused on minimizing the junction resistance between wires. However, there have been no detailed reports on what the junction resistance is, nor is there a known benchmark for the minimum attainable sheet resistance of an optimized network. In this paper, we present junction resistance measurements of individual silver nanowire junctions, producing for the first time a distribution of junction resistance values and conclusively demonstrating that the junction contribution to the overall resistance can be reduced beyond that of the wires through standard processing techniques. We find that this distribution shows the presence of a small percentage (6%) of high-resistance junctions, and we show how these may impact the performance of network-based materials. Finally, through combining experiment with a rigorous model, we demonstrate the important role played by the network skeleton and the specific connectivity of the network in determining network performance.

In this article, we present a comprehensive investigation of the photothermal properties of plasmonic nanowire networks. We measure the local steady-state temperature increase, heat source density, and absorption in Ag, Au, and Ni metallic nanowire networks under optical illumination. This allows direct experimental confirmation of increased heat generation at the junction between two metallic nanowires and stacking-dependent absorption of polarized light. Due to thermal collective effects, the local temperature distribution in a network is shown to be completely delocalized on a micrometer scale, despite the nanoscale features in the heat source density. Comparison of the experimental temperature profile with numerical simulation allows an upper limit for the effective thermal conductivity of a Ag nanowire network to be established at 43 Wm(-1) K(-1) (0.1 κbulk).

We describe the fabrication, operation principles, and simulation of a coherent single-atom quantum interference device (QID) structure on Si(100) controlled by the properties of single atoms. The energy and spatial distribution of the wave functions associated with the device are visualized by scanning tunneling spectroscopy and the amplitude and phase of the evanescent wave functions that couple into the quantum well states are directly measured, including the action of an electrostatic gate. Density functional theory simulations were employed to simulate the electronic structure of the device structure, which is in excellent agreement with the measurements. Simulations of device transmission demonstrate that our coherent single-atom QID can have ON-OFF ratios in excess of 10(3) with potentially minimal power dissipation.

Nanoscale devices that are sensitive to measurement history enable memory applications, and memristors are currently under intense investigation for robustness and functionality. Here we describe the fabrication and performance of a memristor-like device that comprises a single TiO2 nanowire in contact with Au electrodes, demonstrating both high sensitivity to electrical stimuli and high levels of control. Through an electroforming process, a population of charged dopants is created at the interface between the wire and electrode that can be manipulated to demonstrate a range of device and memristor characteristics. In contrast to conventional two-terminal memristors, our device is essentially a diode that exhibits memristance in the forward bias direction. The device is easily reset to the off state by a single voltage pulse and can be incremented to provide a range of controllable conductance states in the forward direction. Electrochemical modification of the Schottky barrier at the electrodes is proposed as an underlying mechanism, and six-level memory operations are demonstrated on a single nanowire.

Networks comprised of randomly oriented overlapping nanowires offer the possibility of simple fabrication on a variety of substrates, in contrast with the precise placement required for devices with single or aligned nanowires. Metal nanowires typically have a coating of surfactant or oxide that prevents aggregation, but also prevents electrical connection. Prohibitively high voltages can be required to electrically activate nanowire networks, and even after activation many nanowire junctions remain nonconducting. Nonelectrical activation methods can enhance conductivity but destroy the memristive behavior of the junctions that comprise the network. We show through both simulation and experiment that electrical stimulation, microstructured electrode geometry, and feature scaling can all be used to manipulate the connectivity and thus electrical conductivity of networks of silver nanowires with a nonconducting polymer coating. More generally, these results describe a strategy to integrate nanomaterials into controllable, adaptive macroscale materials.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Connectivity in metallic nanowire networks with resistive junctions is manipulated by applying an electric field to create materials with tunable electrical conductivity. In situ electron microscope and electrical measurements visualize the activation and evolution of connectivity within these networks. Modeling nanowire networks, having a distribution of junction breakdown voltages, reveals universal scaling behavior applicable to all network materials. We demonstrate how local connectivity within these networks can be programmed and discuss material and device applications.

LiMo(3)Se(3) is a highly anisotropic solid comprised of a regular pattern of quasi-1-D wire-like structures. Solutions of LiMo(3)Se(3) deposited on substrates and TEM grids reveal the presence of two-dimensional network morphologies. High resolution STEM imaging reveals that the junctions within these networks are not formed by discrete overlying LiMo(3)Se(3) fibers or wires. Rather the junctions are continuous in that the wires are seamlessly interwoven from one bundle to the next. We investigated network formation by dynamic light scattering and AFM and demonstrate that the networks are not pre-existent in solution but rather form via self-assembly of nanoscale building blocks that is driven by solvent evaporation.

Standard surface energy balances using literature values for pure liquids predict that water droplets are unstable at the liquid/air interfaces of many common organic solvents. While the behavior of macroscopic drops in the presence of solvents has been studied, the study of droplets in the micrometer size regime and the possible role of line tension are notably absent. In this article, we experimentally investigate the existence and stability of such micrometer-scale droplets formed at air/solvent interfaces and the possible roles played by partial solubility of organic liquids in water and solvent migration in the lowering of the key air/water surface tension. Three solvents are studied: toluene, butyl acetate, and chloroform, using a technique to optically monitor both condensation and manual deposition of water microdroplets onto air/solvent surfaces. This demonstrates both the existence of stable water droplets and allows measurement of the contact angles at the solvent/water/air interface. Contact angles are shown to be independent of droplet size (diameters: 2-30 μm), ruling out a line tension stabilization mechanism for droplets of radii greater than 1 μm. The interfacial tensions of the deposited water droplets are independently measured using an equivalent macroscopic experiment, which yield results consistent with the partial miscibility of toluene and butyl acetate in water. A discrepancy is observed for chloroform, for which possible mechanisms are discussed.

We consider the reaction of 1,3-cyclohexadiene (1,3-CHD) on Si(100) and show that the observed reactivity and stereoselectivity cannot be explained on the basis of thermodynamics. We postulate the existence of secondary orbital interactions (SOIs) and introduce a simple algorithm that examines all possible secondary interactions between the frontier orbitals of the molecule and the surface. We demonstrate using an orbital symmetry-based algorithm supported by DFT calculations that SOIs favor a particular molecular configuration, consistent with the experimental observations. The potential role of SOIs in controlling surface chemical reactions is discussed.

Metal-seeded growth of one-dimensional (1D) semiconductor nanostructures is still a very active field of research, despite the huge progress which has been made in understanding this fundamental phenomenon. Liquid growth promoters allow control of the aspect ratio, diameter, and structure of 1D crystals via external parameters, such as precursor feedstock, temperature, and operating pressure. However the transfer of crystallographic information from a catalytic nanoparticle seed to a growing nanowire has not been described in the literature. Here we define the theoretical requirements for transferring defects from nanoparticle seeds to growing semiconductor nanowires and describe why Ag nanoparticles are ideal candidates for this purpose. We detail in this paper the influence of solid Ag growth seeds on the crystal quality of Ge nanowires, synthesized using a supercritical fluid growth process. Significantly, under certain reaction conditions {111} stacking faults in the Ag seeds can be directly transferred to a high percentage of <112>-oriented Ge nanowires, in the form of radial twins in the semiconductor crystals. Defect transfer from nanoparticles to nanowires could open up the possibility of engineering 1D nanostructures with new and tunable physical properties and morphologies.

We introduce a novel wire growth technique that involves simply heating a multilayer film specifically designed to take advantage of the different surface energies of the substrate and film components. In all cases the high surface energy component is extruded as a single crystal nanowire. Moreover we demonstrate that patterning the bilayer film generates localized surface agglomeration waves during the anneal that can be exploited to position the grown wires. Examples of Au and Cu nanowire growth are presented, and the generalization of this method to other systems is discussed.

Conductance imaging atomic force microscopy was used to probe the electrical interface between single-walled carbon nanotubes and metal electrodes. The contact resistance was optimized by applying a local voltage pulse (approximately 2 s) using a conductive probe with controlled loading force to the region of the metal electrode contacting the nanotube. Using this technique, we show that Pd forms superior contacts, resulting in contact resistance values that are among the lowest ever reported.

Transport in single-walled carbon nanotubes (SWCNTs) networks is shown to be dominated by resistance at network junctions which scale with the size of the interconnecting bundles. Acid treatment, known to dope individual tubes, actually produces a dramatic reduction in junction resistances, whereas annealing significantly increases this resistance. Measured junction resistances for pristine, acid-treated and annealed SWCNT bundles correlate with conductivities of the corresponding films, in excellent agreement with a model in which junctions control the overall network performance.

We have used aqueous dispersions of silver nanowires to prepare thin, flexible, transparent, conducting films. The nanowires are of length and diameter close to 6.5 μm and 85 nm, respectively. At low thickness, the films consist of networks but appear to become bulk-like for mean film thicknesses above ∼160 nm. These films can be very transparent with optical transmittance reaching as high as 92% for low thickness. The transmittance (550 nm) decreases with increasing thickness, consistent with an optical conductivity of 6472 S/m. The films are also very uniform; the transmittance varies spatially by typically <2%. The sheet resistance decreases with increasing thickness, falling below 1 Ω/◻ for thicknesses above 300 nm. The DC conductivity increases from 2 × 10(5) S/m for very thin films before saturating at 5 × 10(6) S/m for thicker films. Similarly, the ratio of DC to optical conductivity increases with increasing thickness from 25 for the thinnest films, saturating at ∼500 for thicknesses above ∼160 nm. We believe this is the highest conductivity ratio ever observed for nanostructured films and is matched only by doped metal oxide films. These nanowire films are electromechanically very robust, with all but the thinnest films showing no change in sheet resistance when flexed over >1000 cycles. Such results make these films ideal as replacements for indium tin oxide as transparent electrodes. We have prepared films with optical transmittance and sheet resistance of 85% and 13 Ω/◻, respectively. This is very close to that displayed by commercially available indium tin oxide.

We have prepared flexible, transparent, and very conducting thin composite films from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), filled with both arc discharge and HIPCO single-walled nanotubes, at high loading level. The films are of high optical uniformity. The arc discharge nanotube-filled composites were significantly more conductive, demonstrating DC conductivities of >10(5) S/m for mass fractions >50 wt %. The ratio of DC to optical conductivity was higher for composites with mass fractions of 55-60 wt % than for nanotube-only films. For an 80 nm thick composite, filled with 60 wt % arc discharge nanotubes, this conductivity ratio was maximized at sigma(DC)/sigma(Op) = 15. This translates into transmittance (550 nm) and sheet resistance of 75 and 80 Omega/square, respectively. These composites were electromechanically very stable, showing <1% resistance change over 130 bend cycles.

Semiconducting nanowires (NWs) are important "building blocks" for potential electrical and electromechanical devices. Here, we report on the mechanical properties of supercritical fluid-grown Ge NWs with radii between 20 and 80 nm. An analysis of the bending and tensile stresses during deformation and failure reveals that while the NWs have a Young's modulus comparable to the bulk value, they have an ultimate strength of 15 GPa, which is the maximum theoretical strength of these materials. This exceptional strength is the highest reported for any conventional semiconductor material and demonstrates that these NWs are without defect or flaws that compromise the mechanical properties.

We present a study that maps out chemical bond formation between a Pt-inked probe and a single 1,3-cyclohexadiene (1,3-CHD) molecule on Si(100). By separating the mechanical and electronic contributions to the current during the approach to contact, we show that there are significant forces between the probe and the C=C of the molecule and we track the relaxation of the molecule, the emergence of a chemical bond feature in the LDOS, and the quenching of specific molecular vibrations during bond formation.

We report a model of nanowire (NW) mechanics that describes force vs displacement curves over the entire elastic range for diverse wire systems. Due to the clamped-wire measurement configuration, the force response in the linear elastic regime can be linear or nonlinear, depending on the system and the wire displacement. For Au NWs the response is essentially linear since yielding occurs prior to the onset of the inherent nonlinearity, while for Si NWs the force response is highly nonlinear, followed by brittle fracture. Since the method describes the entire range of elastic deformation, it unequivocally identifies the yield points in both of these materials.

To exploit the novel size-dependent mechanical properties of nanowires, it is necessary for one to develop strategies to control the strength and toughness of these materials. Here, we report on the mechanical properties of silver nanowires with a unique fivefold twin structure using a lateral force atomic force microscopy (AFM) method in which wires are held in a double-clamped beam configuration. Force-displacement curves exhibit super elastic behavior followed by unexpected brittle failure without significant plastic deformation. Thermal annealing resulted in a gradual transition to weaker, more ductile materials associated with the elimination of the twinned boundary structure. These results point to the critical roles of microstructure and confinement in engineering the mechanical properties of nanoscale materials.