Tip Growth of Quasi-Metallic Bilayer Graphene Nanoribbons with Armchair Chirality.

Graphene nanoribbons (GNRs), quasi one-dimensional (1D) narrow strips of graphene, have shown promise for high-performance nanoelectronics due to their exceptionally high carrier mobility and structurally tunable bandgaps. However, producing chirality-uniform GNRs on insulating substrates remains a big challenge. Here, we report the successful growth of bilayer GNRs with predominantly armchair chirality and ultranarrow widths (<5 nm) on insulating hexagonal boron nitride (h-BN) substrates using chemical vapor deposition (CVD). The growth of GNRs is catalyzed by transition metal nanoparticles, including Fe, Co, and Ni, through a unique tip-growth mechanism. Notably, GNRs catalyzed by Ni exhibit a high purity (97.3%) of armchair chirality. Electron transport measurements indicate that the ultrathin bilayer armchair GNRs exhibit quasi-metallic behavior. This quasi-metallicity is further supported by density functional theory (DFT) calculations, which reveal a significantly reduced bandgap in bilayer armchair GNRs. The chirality-specific GNRs reported here offer promising advancements for the application of graphene in nanoelectronics.

Energetically Favored 2D to 3D Transition: Why Silicene Cannot Be Grown on Ag(111).

Silicene, a two-dimensional (2D) Si monolayer with properties similar to those of graphene, has attracted considerable attention because of its compatibility with existing technology. Most growth efforts to date have focused on the Ag(111) substrate, with a 3 × 3 phase widely reported below one monolayer (ML). As the coverage increases, a √3 × âˆš3 pattern frequently emerges, which has been proposed by various experimental investigations as a Si(111)-3×3-Ag reconstructed structure. We report first-principles calculations to understand this series of observations. A major finding from our energetics studies is that Si growth on Ag(111) beyond one ML will switch to the Volmer-Weber mode, forming three-dimensional sp3 films. Combining with the condition that the 3 × 3 monolayer on Ag(111) does not have the correct buckling pattern of freestanding silicene, we conclude that silicene cannot be grown on Ag(111) and that a 2D to 3D transition is energetically favored beyond one ML.

Metal-Free Electron Donor-Acceptor Pair Enabled Long-Term Stability of Li-CO2 Battery.

The challenges of Lithium-carbon dioxide (Li-CO2) batteries for ensuring long-term cycling stability arise from the thermodynamically stable and electrically insulating discharge products (e.g., Li2CO3), which primarily rely on their interaction with the active materials. To achieve the optimized intermediates, the bifunctional electron donor-acceptor (D-A) pairs are proposed in cathode design to adjust such interactions in the case of B-O pairs. The inclusion of BC2O sites allows for the optimized redistribution of electrons via p-π conjugation. The as-obtained DO-AB pairs endow the enhanced interactions with Li+, CO2, and various intermediates, accompanied by the adjustable growth mode of Li2CO3. The shift from solvation-mediated mode into surface absorption mode in turn manipulates the morphology and decomposition kinetics of Li2CO3. Therefore, the corresponding Li-CO2 battery got twofold improved in both the capacity and reversibility. The cycling prolongs exceed 1300 h and well operates at a wide temperature range (20-50 °C) and different folding angles (0-180°). Such a strategy of introducing electron donor-acceptor pairs provides a distinct direction to optimize the lifetime of Li-CO2 battery from local structure regulation at the atomic scale, further inspiring in-depth understandings for developing electrochemical energy storage and carbon capture technologies.

Simulation and Experiment for Growth of High-Quality and Large-Size AlN Seed Crystals by Spontaneous Nucleation.

Seed crystals are the prerequisite for the growth of high quality and large size aluminum nitride (AlN) single crystal boules. The physical vapor transport (PVT) method is adopted to grow AlN seed crystal. However, this method is not available in nature. Herein, the temperature field distribution in the PVT furnace was simulated using the numerical analysis method to obtain free-standing and large-size seeds. The theoretical studies indicate that the temperature distribution in the crucible is related to the crucible height. According to the theory of growth dynamics and growth surface dynamics, the optimal thermal distribution was achieved through the design of a specific crucible structure, which is determined by the ratio of top-heater power to main-heater power. Moreover, in our experiment, a sole AlN single crystal seed with a length of 12 mm was obtained on the tungsten (W) substrate. The low axial temperature gradient between material source and substrate can decrease the nucleation rate and growth rate, and the high radial temperature gradient of the substrate can promote the expansion of crystal size. Additionally, the crystallinity of the crystals grown under different thermal field conditions are analyzed and compared. The Raman results manifest the superiority of the thermal inversion method in the growth of high quality AlN single crystal.

An Unprecedented Kernel Growth Mode and Layer-Number-Odevity-Dependent Properties in Gold Nanoclusters.

Kernel atoms of Au nanoclusters are packed layer-by-layer along the [001] direction with every full (001) monolayer composed of 8 Au atoms (Au8 unit) in nanoclusters with formula of Au8n+4 (TBBT)4n+8 (n is the number of Au8 units; TBBTH=4-tert-butylbenzenelthiol). It is unclear whether the kernel atoms can be stacked in a defective-layer way along the [001] direction during growth of the series of nanoclusters and how the kernel layer number affects properties. Now, a nanocluster is synthesized that is precisely characterized by mass spectrometry and single-crystal X-ray crystallography, revealing a layer stacking mode in which a half monolayer composed of 4 atoms (Au4 unit) is stacked on the full monolayer along the [001] direction. The size and the odevity of the kernel layer number influence the properties (polarity, photoluminescence) of gold nanoclusters. The obtained nanocluster extends the previous formula from Au8n+4 (TBBT)4n+8 to Au4n+4 (TBBT)2n+8 (n is the number of Au4 units).

Biodegradation of fenpropathrin by Rhodopseudomonas sp. strain PSB07-21 cultured under three different growth modes.

This study aimed at the biodegradation of fenpropathrin by Rhodopseudomonas sp. strain PSB07-21 cultured under different growth modes. The biomass production, cell surface hydrophobicity and fenpropathrin biodegradation efficiency of the strain PSB07-21 cultured under the photoheterotrophic growth mode were better than that shown by the strain PSB07-21 cultured under the photoautotrophic or the chemotrophic growth mode. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis using cell-free protein extracts showed several distinct protein bands in the gels representing the strain PSB07-21 cultured under the photoheterotrophic growth mode. The fenpropathrin enzymatic degradation was clearly affected the bacterial growth mode. Results obtained from this study should improve our knowledge regarding fenpropathrin biodegradation under field conditions. Our findings can also be used to optimize the usage of Rhodopseudomonas sp. PSB07-21 in field applications.

Analogous biomineralization processes between the fossil coral Calceola sandalina (Rugosa, Devonian) and other Recent and fossil cnidarians.

The current work represents a distinctive study about the biomineral properties of exceptionally good preserved skeletons of Calceola sandalina from the Middle Devonian of Couvin (Belgium), Smara (Morocco) and (Algeria) and their relation in the evolution of biomineralization of cnidarians. Structural and crystallographic analyses of the skeletons have been done by petrographic microscopy, electron scanning microscopy (SEM), atomic force microscopy (AFM), electron backscatter diffraction (EBSD), computer-integrated polarization microscopy (CIP) and electron microprobe analysis (EMPA). Calceola skeletons have many similarities with other cnidarians, mainly with other Palaeozoic corals as Syringoporicae: The microcrystals are composed of co-oriented nanocrystals that remind to mesocrystals, suggesting a biocrystallization process by particle attachment (CPA). The relationship between the nanocrystals and microcrystals suggest a growth mode similar to mineral bridges. A similar model was described for Syringoporicae corals (Tabulata) and it is similar to the coordinated-growth mode described in scleractinians and molluscs. Calceola skeletons show also a convergent structure with scleractinian forming Rapid Accretion Deposits (RAD), which share some structural and chemical properties. These evidences suggest analogous processes of biomineralization derived from a stem group of cnidarians. The results of this paper highlight the value of biomineralization studies in fossil organisms to understand the evolution of biomineralization mechanism through Phanerozoic.

Growth of large-scale boron nanowire patterns with identical base-up mode and in situ field emission studies of individual boron nanowire.

Boron nanowires (BNWs) are considered as an ideal optoelectronic nanomaterial, but controlling them in identical growth mode and large-area patterns is technically challenging. Here, large-scale BNW patterns with a uniform base-up growth mode are successfully fabricated by choosing Ni film as the catalyst. Moreover, they exhibit low turn-on field (4.3 V/µm) and excellent field emission uniformity (88%).

Probing microscale crystallization phenomena: Transforming waste slags into riches.

Metal smelting and combustion of solid fuels produce significant quantities of waste slag, leading to issues such as land occupation and environmental pollution. Understanding and controlling the microscale crystallization phenomena of these slags during thermal treatment is crucial for transforming waste slags into materials suitable for carbon capture or glass ceramics. Previous research has primarily focused on macroscopic crystallization behaviors, significantly advancing the utilization of waste slags in cement clinker production. However, macroscopic results are inadequate for precisely controlling the microscale crystallization behaviors of waste slags. Here, we employed the single hot thermocouple technique to visually explore crystal growth modes, shapes, sizes, numbers, and translational rates of the crystal growth front in a representative blast furnace slag under various isothermal temperatures. The results revealed that crystals exhibited five modes as the isothermal temperature gradually increased, including equiaxed, equiaxed & columnar, columnar, columnar & planar, and planar. Moreover, the translational rate of the crystal growth front increased from 0.011 µm·s-1 to 43.7 µm·s-1 with an increase in the isothermal temperature. Simultaneously, the number of crystals decreased from around 104 to 100 µm-2. On this basis, correlations between microscale crystallization behaviors and isothermal temperature were established to fill the current gap.

Effect of Titanium Dioxide Particles on the Thermal Stability of Silica Aerogels.

Silica aerogels exhibit a unique nanostructure with low thermal conductivity and low density, making them attractive materials for thermal isolation under extreme conditions. The TiO2 particle is one of the common industrial additives used to reduce the thermal radiation of aerogel composites under high-temperature environments, but its influence on thermal resistance is almost unknown. Herein, we report the effect of TiO2 nanoparticles with different crystal phases and different sizes on the thermal stability of silica aerogel composites. By adding TiO2 nanoparticles, the aerogel can significantly resist collapse at high temperatures (up to 1000 °C). And compared with the rutile phase TiO2, the anatase phase TiO2 shows much higher temperature resistance performance, with shrinkage of only one-sixth of the rutile phase after 800 °C treatment. Interestingly, energy-dispersive spectrometer mapping results show that after 800 °C treatment, silica nanoparticles (NPs) are squeezed out in between anatase TiO2 particles, which resists the coarsening of silica NPs and ultimately enhances the stability of aerogel composites. The optimal anatase phase TiO2-doped silica aerogel demonstrates the integrated properties of crack-free morphology (2.84% shrinkage), low thermal conductivity (29.30 mW/(m·K)) and low density (149.4 mg/cm3) after 800 °C treatment. This study may provide new insights for developing oxide-doped silica aerogels with both high-temperature resistance and low thermal radiation.

Modulation of Remote Epitaxial Heterointerface by Graphene-Assisted Attenuative Charge Transfer.

Remote epitaxy (RE), substrate polarity can "penetrate" two-dimensional materials (2DMs) and act on the epi-layer, showing a prospective universal growth strategy. However, essentially, the role that 2DMs plays in RE has not been deeply investigated so far. Here, the RE of single-crystal films on the weakest polarity/iconicity substrate is realized to reveal its essence physical properties. Graphene facilitates attenuative charge transfer (ACT) from a substrate to epi-layer to construct remote interactions. Interfacial atoms are assembled into "incommensurate" epitaxial relationships through graphene to reduce misfit dislocations in the epi-layer. Moreover, graphene reduces the atomic migration barrier, leading to a tendency toward a "layer-by-layer" growth mode. Such film growth mode is different with the conventional epitaxy (CE), and it is beneficial for the fast growth of epi-layers and the reduction of dislocations at coalescence boundaries. The insightful revelation of the role of graphene reveals the interface physics of RE and provides a more valuable guide to using 2DMs to expand three-dimensional materials (3DMs) for application in devices.

Construction of Hollow Carbon Nanofibers with Graphene Nanorods as Nano-Antennas for Lower-Frequency Microwave Absorption.

Electromagnetic (EM) wave absorbers at a lower-frequency region (2-8 GHz) require higher attenuation ability to achieve efficient absorption. However, the impedance match condition and attenuation ability are usually inversely related. Herein, one-dimensional hollow carbon nanofibers with graphene nanorods are prepared based on coaxial electrospinning technology. The morphology of graphene nanorods can be controlled by the annealing process. As the annealing time increased from 2 to 8 h, graphene nanospheres grew into graphene nanorods, which were catalyzed by Co catalysts derived from ZIF-67 nanoparticles. These nanorods can play the role of nano-antennas, which can guide EM waves into materials to enhance impedance match conditions. As a result, the carbon nanofibers with graphene nanorods possess a larger impedance match area with higher attenuation ability. The minimum reflection loss reaches -57.1 dB at a thickness of 4.6 mm, and the effective absorption bandwidth can cover almost both the S and C bands (2.4-8 GHz). This work contributes a meaningful perspective into the modulation of microwave absorption performance in the lower-frequency range.

Single-Crystalline Pyramidal TiCx Particles Grown by Biphase Diffusion Synthesis.

In this study, we present single-crystalline pyramid-shaped (SP) TiCx particles synthesized on a stacked melt (copper)-solid (titanium) substrate using a biphase diffusion synthesis (BDS) method, in which different sizes ranging from nano- to micrometer scale were obtained within the copper melt with the {100} planes exposed to air. Direct observation and further plasma treatment of the pyramids at different self-assembly stages facilitated the investigation of their growth mode, especially in the horizontal plane. The dendritic growth mode along with the edge and corner-shared modes of the SP TiCx particles frozen on the copper surface was investigated. With SP TiCx particles stacked on top, MoS2-based phototransistors exhibited an up to 6-fold photocurrent increase under laser illumination at different wavelengths, which was attributed to the localized surface plasmonic resonance (LSPR) effect. The BDS method is applied for the synthesis of SP TiCx particles, with a detailed investigation of the relevant growth mode and related applications, such as decoration for high-performance photodevices.

Effect of Local Topography on Cell Division of Staphylococcus spp.

Surface engineering is a promising strategy to limit or prevent the formation of biofilms. The use of topographic cues to influence early stages of biofilm formationn has been explored, yet many fundamental questions remain unanswered. In this work, we develop a topological model supported by direct experimental evidence, which is able to explain the effect of local topography on the fate of bacterial micro-colonies of Staphylococcus spp. We demonstrate how topological memory at the single-cell level, characteristic of this genus of Gram-positive bacteria, can be exploited to influence the architecture of micro-colonies and the average number of surface anchoring points over nano-patterned surfaces, formed by vertically aligned silicon nanowire arrays that can be reliably produced on a commercial scale, providing an excellent platform to investigate the effect of topography on the early stages of Staphylococcus spp. colonisation. The surfaces are not intrinsically antimicrobial, yet they delivered a topography-based bacteriostatic effect and a significant disruption of the local morphology of micro-colonies at the surface. The insights from this work could open new avenues towards designed technologies for biofilm engineering and prevention, based on surface topography.

Collision Electrochemical Synthesis of Metal Nanoparticles Using Electrons as Green Reducing Agent.

Synthesis of high-quality metal nanoparticles (NPs) is the premise toward their downstream diverse applications. Although some electrochemical synthesis strategies have been developed, the necessary use of high-concentration electrolyte solution as current pathway and reaction medium severely limits the colloidal stability of the growing NPs in the solution and their tunability in size and shape. Herein, we report a collision electrochemical method for the synthesis of metal NPs without the use of electrolyte solution. To this end, we designed an asymmetrical electrochemical cell to control the potential (i.e., to supply electrons) in the reaction system via a separated electrochemical cell, thereby enabling the electrochemical reaction occurring in an electrolyte-free growth solution. Consequently, this collision electrochemical method, using seed-mediated growth of NPs as examples, allows the synthesis of monodisperse homogeneous Au NPs and heterogeneous Pd- and Pt-coated Au NPs at a yield comparable to that achieved in common chemical synthesis. Furthermore, this method allows readily tailoring the morphology of the resultant metal NPs just by changing the concentration of the growth solution. Therefore, our green synthesis method is important for a variety of nanomaterials beyond metal NPs.

Multiscale Kinetic Monte Carlo Simulation of Self-Organized Growth of GaN/AlN Quantum Dots.

A three-dimensional kinetic Monte Carlo methodology is developed to study the strained epitaxial growth of wurtzite GaN/AlN quantum dots. It describes the kinetics of effective GaN adatoms on an hexagonal lattice. The elastic strain energy is evaluated by a purposely devised procedure: first, we take advantage of the fact that the deformation in a lattice-mismatched heterostructure is equivalent to that obtained by assuming that one of the regions of the system is subjected to a properly chosen uniform stress (Eshelby inclusion concept), and then the strain is obtained by applying the Green's function method. The standard Monte Carlo method has been modified to implement a multiscale algorithm that allows the isolated adatoms to perform long diffusion jumps. With these state-of-the art modifications, it is possible to perform efficiently simulations over large areas and long elapsed times. We have taylored the model to the conditions of molecular beam epitaxy under N-rich conditions. The corresponding simulations reproduce the different stages of the Stranski-Krastanov transition, showing quantitative agreement with the experimental findings concerning the critical deposition, and island size and density. The influence of growth parameters, such as the relative fluxes of Ga and N and the substrate temperature, is also studied and found to be consistent with the experimental observations. In addition, the growth of stacked layers of quantum dots is also simulated and the conditions for their vertical alignment and homogenization are illustrated. In summary, the developed methodology allows one to reproduce the main features of the self-organized quantum dot growth and to understand the microscopic mechanisms at play.

Dependence of the Growth Mode in Epitaxial FePt Films on Surface Free Energy.

Epitaxial thin films of L10-ordered FePt alloys are one of the most important materials in magnetic recording and spintronics applications due to their large perpendicular magnetic anisotropy (PMA). The key to the production of these required superior properties lies in the control of the growth mode of the films. Further, it is necessary to distinguish between the effect of lattice mismatch and surface free energy on the growth mode because of their strong correlation. In this study, the effect of surface free energy on the growth mode of FePt epitaxial films was investigated using MgO, NiO, and MgON surfaces with almost the same lattice constant to exclude the effect of lattice mismatch. It was found that the growth mode can be tuned from a three-dimensional (3D) island mode on MgO to a more two-dimensional (2D)-like mode on MgON and NiO. Contact angle measurements revealed that MgON and NiO show larger surface free energy than MgO, indicating that the difference in the growth mode is due to their larger surface free energy. In addition, MgON was found to induce not only a flat surface as FePt grown on SrTiO3 (STO), which has a small lattice mismatch, but also a larger PMA than that of STO/FePt. As larger lattice mismatch is favored to induce a higher PMA into the FePt films, MgO substrates are exclusively used, but 3D island growth is indispensable. This work demonstrates that tuning the surface free energy enables us to achieve a large PMA and flat film surface in FePt epitaxial films on MgO. The results also indicate that modifying the surface free energy is pertinent for the flexible functional design of thin films.

Balanced Ambipolar Charge Transport in Phenacene/Perylene Heterojunction-Based Organic Field-Effect Transistors.

Electronic devices relying on the combination of different conjugated organic materials are considerably appealing for their potential use in many applications such as photovoltaics, light emission, and digital/analog circuitry. In this study, the electrical response of field-effect transistors achieved through the evaporation of picene and PDIF-CN2 molecules, two well-known organic semiconductors with remarkable charge transport properties, was investigated. With the main goal to get a balanced ambipolar response, various device configurations bearing double-layer, triple-layer, and codeposited active channels were analyzed. The most suitable choices for the layer deposition processes, the related characteristic parameters, and the electrode position were identified to this purpose. In this way, ambipolar organic field-effect transistors exhibiting balanced mobility values exceeding 0.1 cm2 V-1 s-1 for both electrons and holes were obtained. These experimental results highlight also how the combination between picene and PDIF-CN2 layers allows tuning the threshold voltages of the p-type response. Scanning Kelvin probe microscopy (SKPM) images acquired on picene/PDIF-CN2 heterojunctions suggest the presence of an interface dipole between the two organic layers. This feature is related to the partial accumulation of space charge at the interface being enhanced when the electrons are depleted in the underlayer.

Growth Mode and Physiological State of Cells Prior to Biofilm Formation Affect Immune Evasion and Persistence of Staphylococcus aureus.

The present study investigated Staphylococcus aureus ATCC25923 surfaceomes (cell surface proteins) during prolonged growth by subjecting planktonic and biofilm cultures (initiated from exponential or stationary cells) to label-free quantitative surfaceomics and phenotypic confirmations. The abundance of adhesion, autolytic, hemolytic, and lipolytic proteins decreased over time in both growth modes, while an opposite trend was detected for many tricarboxylic acid (TCA) cycle, reactive oxygen species (ROS) scavenging, Fe-S repair, and peptidolytic moonlighters. In planktonic cells, these changes were accompanied by decreasing and increasing adherence to hydrophobic surface and fibronectin, respectively. Specific RNA/DNA binding (cold-shock protein CspD and ribosomal proteins) and the immune evasion (SpA, ClfA, and IsaB) proteins were notably more abundant on fully mature biofilms initiated with stationary-phase cells (SDBF) compared to biofilms derived from exponential cells (EDBF) or equivalent planktonic cells. The fully matured SDBF cells demonstrated higher viability in THP-1 monocyte/macrophage cells compared to the EDBF cells. Peptidoglycan strengthening, specific urea-cycle, and detoxification enzymes were more abundant on planktonic than biofilm cells, indicating the activation of growth-mode specific pathways during prolonged cultivation. Thus, we show that S. aureus shapes its surfaceome in a growth mode-dependent manner to reach high levofloxacin tolerance (>200-times the minimum biofilm inhibitory concentration). This study also demonstrates that the phenotypic state of the cells prior to biofilm formation affects the immune-evasion and persistence-related traits of S. aureus.

van der Waals Epitaxy of Antimony Islands, Sheets, and Thin Films on Single-Crystalline Graphene.

Antimony (Sb) nanostructures, including islands, sheets, and thin films, of high crystallinity were epitaxially grown on single-crystalline graphene through van der Waals interactions. Two types of graphene substrates grown by chemical vapor deposition were used, the as-grown graphene on Cu(111)/ c-sapphire and the transferred graphene on SiO2/Si. On the as-grown graphene, deposition of ultrathin Sb resulted in two growth modes and associated morphologies of Sb. One was Sb islands grown in Volmer-Weber (VW) mode, and the other was Sb sheets grown in Frank-van der Merve (FM) mode. In contrast, only Sb islands grown in VW mode were found in a parallel growth experiment on the transferred graphene. The existence of Sb sheets on the as-grown graphene was attributed to the remote epitaxy between Sb and Cu underneath the graphene. In addition, Sb thin films were grown on both the as-grown and transferred graphene substrates. Both films indicated high quality, and no significant difference can be found between these two films. This work unveiled two epitaxial alignments between Sb(0001) and graphene, namely, Sb [101̅0]∥graphene [10] for Sb islands and Sb [21̅1̅0]∥graphene [10] for Sb sheets. For Sb thin films on graphene, the epitaxial alignment followed that of Sb islands, implying that Sb thin films originated from the continued growth of Sb islands. Last, Raman spectroscopy was used to probe the state of graphene under ultrathin Sb. No strain, doping, or disorder was found in the graphene postgrowth of Sb. The knowledge of the interface formation between ultrathin Sb and graphene provides a valuable foundation for future research on van der Waals heterostructures between antimonene and graphene.