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Monolayer graphene with nanometre-scale pores, atomically thin thickness and remarkable mechanical properties provides wide-ranging opportunities for applications in ion and molecular separations1, energy storage2 and electronics3. Because the performance of these applications relies heavily on the size of the nanopores, it is desirable to design and engineer with precision a suitable nanopore size with narrow size distributions. However, conventional top-down processes often yield log-normal distributions with long tails, particularly at the sub-nanometre scale4. Moreover, the size distribution and density of the nanopores are often intrinsically intercorrelated, leading to a trade-off between the two that substantially limits their applications5-9. Here we report a cascaded compression approach to narrowing the size distribution of nanopores with left skewness and ultrasmall tail deviation, while keeping the density of nanopores increasing at each compression cycle. The formation of nanopores is split into many small steps, in each of which the size distribution of all the existing nanopores is compressed by a combination of shrinkage and expansion and, at the same time as expansion, a new batch of nanopores is created, leading to increased nanopore density by each cycle. As a result, high-density nanopores in monolayer graphene with a left-skewed, short-tail size distribution are obtained that show ultrafast and ångström-size-tunable selective transport of ions and molecules, breaking the limitation of the conventional log-normal size distribution9,10. This method allows for independent control of several metrics of the generated nanopores, including the density, mean diameter, standard deviation and skewness of the size distribution, which will lead to the next leap in nanotechnology.
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Achieving a low contact resistance has been an important issue in the design of two-dimensional (2D) semiconductor-metal interfaces. The metal contact resistance is dominated by interfacial interactions. Here, we systematically investigate 2D semiconductor-metal interfaces formed by transferring monolayer MoS2 onto prefabricated metal surfaces, such as Au and Pd, using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and Raman spectroscopy. In contrast to the MoS2/HOPG interface, the interfaces of MoS2/Au and MoS2/Pd feature the formation of weak covalent bonds. The XPS spectra reveal distinct peak positions for S-Au and S-Pd, indicating a higher doping concentration at the S-Au interface. This difference is a key factor in understanding the electronic interactions at the metal-MoS2 interfaces. Additionally, we observe that the metal surface roughness is a critical determinant of the adhesion behavior of transferred monolayer MoS2, resulting in different strains and doping concentrations. The strain on transferred MoS2 increases with an increase in substrate roughness. However, the strain is released when the roughness of metal surface surpasses a certain threshold. The dependence of the contact material and the influence of the substrate roughness on the contact interface provide critical information for improving 2D semiconductor-metal contacts and device performance.
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The electric field is an important parameter to vary in a single-molecule experiment, because it can directly affect the charge distribution around the molecule. Yet, performing such an experiment with a well-defined electric field for a model chemical reaction at an interface has proven to be extremely difficult. Here, by combining a graphene field-effect transistor and a gate-tunable scanning tunneling microscope (STM), we reveal how this strategy enables the intramolecular H atom transfer of a metal-free macrocycle to be controlled with an external field. Experiments and theory both elucidate how the energetic barrier to tautomerization decreases with increasing electric field. The consistency between the two results demonstrates the potential in using electric fields to engineer molecular switching mechanisms that are ubiquitous in nanoscale electronic devices.
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TiO2 anatase plays a central role in energy and environmental research. A major bottleneck toward developing artificial photosynthesis with TiO2 is that it only absorbs ultraviolet light, owing to its large bandgap of 3.2 eV. If one could reduce the bandgap of anatase to the visible region, TiO2-based photocatalysis could become a competitive clean energy source. Here, using scanning tunneling microscopy and spectroscopy in conjunction with density functional theory calculations, we report the discovery of a highly reactive titanium-terminated anatase surface with a reduced bandgap of less than 2 eV, stretching into the red portion of the solar spectrum. By tuning the surface preparation conditions, we can reversibly switch between the standard anatase surface and the newly discovered low bandgap surface phase. The identification of a TiO2 anatase surface phase with a bandgap in the visible and high chemical reactivity has important implications for solar energy conversion, photocatalysis, and artificial photosynthesis.
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Titânio/química , Luz , Microscopia de Tunelamento , Modelos Moleculares , Fotossíntese , Energia Solar , Propriedades de SuperfícieRESUMO
Dye-sensitized solar cells constitute a promising approach to sustainable and low-cost solar energy conversion. Their overall efficiency crucially depends on the effective coupling of the photosensitizers to the photoelectrode and the details of the dye's energy levels at the interface. Despite great efforts, the specific binding of prototypical ruthenium-based dyes to TiO2, their potential supramolecular interaction, and the interrelation between adsorption geometry and electron injection efficiency lack experimental evidence. Here we demonstrate multiconformational adsorption and energy level alignment of single N3 dyes on TiO2 anatase (101) revealed by scanning tunnelling microscopy and spectroscopy. The distinctly bound molecules show significant variations of their excited state levels associated with different driving forces for photoelectron injection. These findings emphasize the critical role of the interfacial coupling and suggest that further designs of dye-sensitized solar cells should target a higher selectivity in the dye-substrate binding conformations in order to ensure efficient electron injection from all photosensitizers.
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One of the exotic expectations in the 2D curved spacetime is the geometric potential from the curvature of the 2D space, still possessing unsolved fundamental questions through Dirac quantization. The atomically thin 2D materials are promising for the realization of the geometric potential, but the geometric potential in 2D materials is not identified experimentally. Here, the curvature-induced ring-patterned bound states are observed in structurally deformed 2D semiconductors and formulated the modified geometric potential for the curvature effect, which demonstrates the ring-shape bound states with angular momentum. The formulated modified geometric potential is analogous to the effective potential of a rotating charged black hole. Density functional theory and tight-binding calculations are performed, which quantitatively agree well with the results of the modified geometric potential. The modified geometric potential is described by modified Gaussian and mean curvatures, corresponding to the curvature-induced changes in spin-orbit interaction and band gap, respectively. Even for complex structural deformation, the geometric potential solves the complexity, which aligns well with experimental results. The understanding of the modified geometric potential provides us with an intuitive clue for quantum transport and a key factor for new quantum applications such as valleytronics, spintronics, and straintronics in 2D semiconductors.
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Quantum fluctuations of wavefunctions in disorder-driven quantum phase transitions (QPT) exhibit criticality, as evidenced by their multifractality and power law behavior. However, understanding the metal-insulator transition (MIT) as a continuous QPT in a disordered system has been challenging due to fundamental issues such as the lack of an apparent order parameter and its dynamical nature. Here, we elucidate the universal mechanism underlying the structural-disorder-driven MIT in 2D semiconductors through autocorrelation and multifractality of quantum fluctuations. The structural disorder causes curvature-induced band gap fluctuations, leading to charge localization and formation of band tails near band edges. As doping level increases, the localization-delocalization transition occurs when states above a critical energy become uniform due to unusual band bending by localized charge. Furthermore, curvature induces local variations in spin-orbit interactions, resulting in non-uniform ferromagnetic domains. Our findings demonstrate that the structural disorder in 2D materials is essential to understanding the intricate phenomena associated with localization-delocalization transition, charge percolation, and spin glass with both topological and magnetic disorders.
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Strain is inevitable in two-dimensional (2D) materials, regardless of whether the film is suspended or supported. However, the direct measurement of strain response at the atomic scale is challenging due to the difficulties of maintaining both flexibility and mechanical stability at low temperature under UHV conditions. In this work, we have implemented a compact nanoindentation system with a size of [Formula: see text] 160 mm[Formula: see text] [Formula: see text] 5.2 mm in a scanning tunneling microscope (STM) sample holder, which enables the reversible control of strain and gate electric field. A combination of gearbox and piezoelectric actuator allowed us to modulate the depth of the indentation continuously with nanometer precision. The 2D materials were transferred onto the polyimide film. Pd clamp was used to enhance the strain transfer from the polyimide from to the 2D layers. Using this unique technique, strain response of graphene lattice were observed at atomic precision. In the relaxed graphene, strain is induced mainly by local curvature. However, in the strained graphene with tented structure, the lattice parameters become more sensitive to the indentor height change and stretching strain is increased additionally. Moreover, the gate controllability is confirmed by measuring the dependence of the STM tip height on gate voltage.
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Single crystal iron nanocubes are produced by simply heating a bilayer film. This surface energy driven growth (SEDG) method exploits the difference in surface energies of the components (γ(Fe) ~ 2.2 J m(-2) versus γ(Nd) ~ 0.7 J m(-2)) in the binary alloy Fe-Nd system to produce nanocubes of the higher energy Fe component. The dimensions of the cubes range from tens to hundreds of nanometers in size and can be controlled by changing the initial thickness of iron in the deposited Fe-Nd bilayer prior to annealing at 700 °C. The composition and structure of the nanocubes was confirmed by transmission electron microscopy analysis as single crystal bcc iron in the α-phase. The cubes were found to exist as core-shell structures with the α-phase encased by an intermetallic Fe-Nd phase, characteristic of the SEDG growth mechanism.
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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.
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The large-area synthesis of high-quality MoS2 plays an important role in realizing industrial applications of optoelectronics, nanoelectronics, and flexible devices. However, current techniques for chemical vapor deposition (CVD)-grown MoS2 require a high synthetic temperature and a transfer process, which limits its utilization in device fabrications. Here, the direct synthesis of high-quality monolayer MoS2 with the domain size up to 120 µm by metal-organic CVD (MOCVD) at a temperature of 320 °C is reported. Owing to the low-substrate temperature, the MOCVD-grown MoS2 exhibits low impurity doping and nearly unstrained properties on the growth substrate, demonstrating enhanced electronic performance with high electron mobility of 68.3 cm2 V-1 s-1 at room temperature. In addition, by tuning the precursor ratio, a better understanding of the MoS2 growth process via a geometric model of the MoS2 flake shape, is developed, which can provide further guidance for the synthesis of 2D materials.
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We introduce a three-way molecular motion which can be a suitable switching system in future molecule-based nanocircuits. A real-space investigation revealed that vinylferrocene adsorbs site-specifically on the Ge(100) surface and then shows a reversible tilting motion, similar to a seesaw. Unlike conventional molecular motions, it not only has three stable switching states at room temperature but also shows a motion-induced surface-structure modification, allowing surface-mediated signal transmission. Demonstrated STM-tip influence on the motion allows the feasibility of tip-induced manipulation.
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The tungsten oxide covered tungsten (W) tip of a scanning tunneling microscope was found to act as a catalyst to catalyze the S-H dissociative adsorption of phenylthiol and 1-octanethiol molecules onto a Ge(100) surface. By varying the distance between the tip and the surface, the area of the tip-catalyzed adsorption could be controlled. We have found that the thiol headgroup is the critical functional group for this catalysis and the catalytic material is the tungsten oxide layer of the tip. This local tip-catalyzed adsorption may be used in positive lithographic methods to produce nanoscale patterning on semiconductor substrates.
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We have studied the adsorption and decomposition of thiophene (C4H4S) on Ge(100) using scanning tunneling microscopy (STM), high-resolution core-level photoemission spectroscopy (HRPES), and density functional theory (DFT) calculation. Analysis of S 2p core-level spectra reveals three adsorption geometries, which we assign to a Ge-S dative bonding state, a [4 + 2] cycloaddition bonding state, and a decomposed bonding state (desulfurization reaction product). Furthermore, we found that the number ratio of the three adsorption geometries depended on the molecular coverage and the annealing temperature. At low coverages, the kinetically favorable dative bonding state is initially formed at room temperature. As the molecular coverage increases, thermodynamically stable [4 + 2] cycloaddition reaction products are additionally produced. In addition, we found that as the surface temperature increased, the [4 + 2] cycloaddition reaction product either possibly desorbed as molecular thiophene or decomposed to form a metallocycle-like species (C4H4Ge2) and a sulfide (Ge2S). We systematically elucidate the changes in the bonding states of adsorbed thiophene on Ge(100) according to the thiophene coverage and annealing temperature.
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The adsorption and decomposition of water on Ge(100) have been investigated using real-time scanning tunneling microscopy (STM) and density-functional theory (DFT) calculations. The STM results revealed two distinct adsorption features of H2O on Ge(100) corresponding to molecular adsorption and H-OH dissociative adsorption. In the molecular adsorption geometry, H2O molecules are bound to the surface via Ge-O dative bonds between the O atom of H2O and the electrophilic down atom of the Ge dimer. In the dissociative adsorption geometry, the H2O molecule dissociates into H and OH, which bind covalently to a Ge-Ge dimer on Ge(100) in an H-Ge-Ge-OH configuration. The DFT calculations showed that the dissociative adsorption geometry is more stable than the molecular adsorption geometry. This finding is consistent with the STM results, which showed that the dissociative product becomes dominant as the H2O coverage is increased. The simulated STM images agreed very well with the experimental images. In the real-time STM experiments, we also observed a structural transformation of the H2O molecule from the molecular adsorption to the dissociative adsorption geometry.
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The adsorption of pyrimidine onto Ge(100) surfaces has been investigated using real-time scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density-functional theory (DFT) calculations. Our results show that the adsorbed pyrimidine molecules are tilted about 40 degrees with respect to the Ge surface, and through a Lewis acid-base reaction form bridges between the down-Ge atoms of neighboring Ge dimer rows by double Ge-N dative bonding without loss of aromaticity. For coverages of pyrimidine up to 0.25 ML, a well-ordered c(4x2) structure results from states that appear in STM micrographs as oval-shaped protrusions, which correspond to pyrimidine molecules datively adsorbed on every other dimer. However, above 0.25 ML, the oval-shaped protrusions gradually change into brighter zigzag lines. At 0.50 ML, a p(2x2) structure results from the states that appear in STM as zigzag lines. The zigzag lines are formed by the attachment of pyrimidine molecules to the down-Ge atoms of every Ge dimer. However, the unstable p(2x2) structure eventually reconstructs into a c(4x2) structure due to steric hindrance between the adsorbed pyrimidine molecules after stopping the exposure of pyrimidine to the surface.
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Germânio/química , Pirimidinas/química , Adsorção , Microscopia de Tunelamento , Modelos Químicos , Tamanho da Partícula , Sensibilidade e Especificidade , Propriedades de Superfície , TemperaturaRESUMO
Extending the resolution and spatial proximity of lithographic patterning below critical dimensions of 20 nm remains a key challenge with very-large-scale integration, especially if the persistent scaling of silicon electronic devices is sustained. One approach, which relies upon the directed self-assembly of block copolymers by chemical-epitaxy, is capable of achieving high density 1 : 1 patterning with critical dimensions approaching 5 nm. Herein, we outline an integration-favourable strategy for fabricating high areal density arrays of aligned silicon nanowires by directed self-assembly of a PS-b-PMMA block copolymer nanopatterns with a L(0) (pitch) of 42 nm, on chemically pre-patterned surfaces. Parallel arrays (5 × 10(6) wires per cm) of uni-directional and isolated silicon nanowires on insulator substrates with critical dimension ranging from 15 to 19 nm were fabricated by using precision plasma etch processes; with each stage monitored by electron microscopy. This step-by-step approach provides detailed information on interfacial oxide formation at the device silicon layer, the polystyrene profile during plasma etching, final critical dimension uniformity and line edge roughness variation nanowire during processing. The resulting silicon-nanowire array devices exhibit Schottky-type behaviour and a clear field-effect. The measured values for resistivity and specific contact resistance were ((2.6 ± 1.2) × 10(5)Ωcm) and ((240 ± 80) Ωcm(2)) respectively. These values are typical for intrinsic (un-doped) silicon when contacted by high work function metal albeit counterintuitive as the resistivity of the starting wafer (â¼10 Ωcm) is 4 orders of magnitude lower. In essence, the nanowires are so small and consist of so few atoms, that statistically, at the original doping level each nanowire contains less than a single dopant atom and consequently exhibits the electrical behaviour of the un-doped host material. Moreover this indicates that the processing successfully avoided unintentional doping. Therefore our approach permits tuning of the device steps to contact the nanowires functionality through careful selection of the initial bulk starting material and/or by means of post processing steps e.g. thermal annealing of metal contacts to produce high performance devices. We envision that such a controllable process, combined with the precision patterning of the aligned block copolymer nanopatterns, could prolong the scaling of nanoelectronics and potentially enable the fabrication of dense, parallel arrays of multi-gate field effect transistors.
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The adsorption structure of glycine on Ge(100) was investigated using scanning tunneling microscopy (STM), density functional theory (DFT) calculations, and high-resolution core-level photoemission spectroscopy (HRCLPES). We found a major adsorption feature of glycine on Ge(100) in the STM images. This feature appeared as a bright protrusion between two dimer rows with a dark adjacent dimer. The position of the bright protrusion located in the middle of the two dimer rows indicates a multibonding adsorption structure. The results of the theoretical calculations confirm that the adsorption structure of glycine on Ge(100) (between two possible multibonding adsorption structures) is an "intrarow O-H dissociated and N dative bonded structure". In the HRCLPES experiments, we found an N 1s peak (at 399.5 eV) and two O 1s peaks (at 531.1 and 532.0 eV), which represent strong evidence that the adsorption configuration of glycine on Ge(100) is composed of both O-H dissociation and N dative bonding. All our STM, DFT, and HRCLPES results suggest that the adsorption structure of glycine molecules on Ge(100) is an "intrarow O-H dissociated and N dative bonded structure".
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Germânio/química , Glicina/química , Adsorção , Microscopia Eletrônica de Varredura , Modelos Moleculares , Estrutura MolecularRESUMO
The adsorption of thiophene on Ge(100) has been studied using scanning tunneling microscopy (STM), high-resolution core-level photoemission spectroscopy (HRPES), and density functional theory (DFT) calculations. Until now, thiophene is known to react with the Ge(100) dimer through a [4 + 2] cycloaddition reaction at room temperature, similar to the case of thiophene on Si(100). However, we found that thiophene has two adsorption geometries on Ge(100) at room temperature, such as a kinetically favorable Ge-S dative bonding configuration and a thermodynamically stable [4 + 2] cycloaddition adduct. Moreover, our STM results show that under 0.25 ML thiophene molecules preferentially produce one-dimensional molecular chain structures on Ge(100) via the Ge-S dative bonding configuration.