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Intrinsic magnetic topological insulators offer low disorder and large magnetic bandgaps for robust magnetic topological phases operating at higher temperatures. By controlling the layer thickness, emergent phenomena such as the Quantum Anomalous Hall (QAH) effect and axion insulator phases have been realised. These observations occur at temperatures significantly lower than the Neel temperature of bulk MnBi2Te4, and measurement of the magnetic energy gap at the Dirac point in ultra-thin MnBi2Te4 has yet to be achieved. Critical to achieving the promise of this system is a direct measurement of the layer-dependent energy gap and verifying whether the gap is magnetic in the QAH phase. Here we utilise temperature dependent angle-resolved photoemission spectroscopy to study epitaxial ultra-thin MnBi2Te4. We directly observe a layer dependent crossover from a 2D ferromagnetic insulator with a bandgap greater than 780 meV in one septuple layer (1 SL) to a QAH insulator with a large energy gap (>100 meV) at 8 K in 3 and 5 SL MnBi2Te4. The QAH gap is confirmed to be magnetic in origin, as it abruptly diminishes with increasing temperature above 8 K. The direct observation of a large magnetic energy gap in the QAH phase of few-SL MnBi2Te4 is promising for further increasing the operating temperature of QAH materials.

The ultrafast monitoring of deoxyribonucleic acid (DNA) dynamic structural changes is an emerging and rapidly growing research topic in biotechnology. The existing optical spectroscopy used to identify different dynamical DNA structures lacks quick response while requiring large consumption of samples and bulky instrumental facilities. It is highly demanded to develop an ultrafast technique that monitors DNA structural changes with the external stimulus or cancer‐related disease scenarios. Here, we demonstrate a novel photonic integrated graphene‐optofluidic device to monitor DNA structural changes with the ultrafast response time. Our approach is featured with an effective and straightforward design of decoding the electronic structure change of graphene induced by its interactions with DNAs in different conformations using ultrafast nanosecond pulse laser and achieving refractive index sensitivity of ~3 × 10−5 RIU. This innovative technique for the first time allows us to perform ultrafast monitoring of the conformational changes of special DNA molecules structures, including G‐quadruplex formation by K+ ions and i‐motif formation by the low pH stimulus. The graphene‐optofluidic device as presented here provides a new class of label‐free, ultrafast, ultrasensitive, compact, and cost‐effective optical biosensors for medical and healthcare applications.

CO2 photoreduction into hydrocarbon fuels is a promising strategy in closing the carbon cycle to realize a sustainable energy economy. Among the many photocatalysts that have been developed thus far, porous graphitic carbon nitride (gC6N6) has emerged as a potential photocatalyst candidate in view of its unique optoelectronic properties, metal-free nature and two-dimensional versatile structure that can be easily modified. In this work, the enhancement of equivalent stoichiometry carbon nitride (gC6N6) through single transition metal atom modification was systematically studied from first principles density functional theory calculations. The formation energy calculations revealed that incorporating single Co, Cu, Ni or Pd atom into gC6N6 is energetically favorable, with the exception of Pt. The computed density of states plot indicates that a greater degree of hybridization of the transition metal atom d-orbitals with the p-orbitals of O atom from CO2 will lead to stronger adsorption interaction. The optical absorption spectra show that Cu, Pd, and Pt promotes greater light absorption by extending the optical absorption to the NIR region. The presence of additional dopant states near the Fermi surface was found to have affected the optical absorption. The band structures of the Co,Cu,Pd,Pt@gC6N6 show bandgap narrowing due to the shifting of conduction band edge closer to the Fermi level. Contrastingly, Ni@gC6N6 exhibits bandgap narrowing through the shifting of the valence band edge to the Fermi level. The band edge positions suggest that anchoring gC6N6 with single Co, Cu, Ni, Pd and Pt atom dopants possesses the capability to reduce CO2 into C1 products. Among all the transition metals studied, Pd@gC6N6 and Cu@gC6N6 are identified as the most promising single-atom photocatalysts for CO2 reduction due to their energetically favorable formation energy, stable CO2 adsorption configuration, narrow bandgap, low charge carrier recombination, extended light absorption range and suitable band edge positions.

Lithium metal has been intensively investigated as a promising anode for next generation rechargeable Li metal batteries (LMBs). However, the safety concern on Li anodes caused by uncontrolled Li dendrite growth in liquid electrolytes hinders their application. Herein, a novel poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) based gel polymer electrolyte (GPE) with an asymmetric structure has been designed and developed to effectively retard the growth of lithium dendrites. Atomistic simulations confirm the strong interactions between PF6− and dipoles in the polymer matrix, which can anchor PF6− in the GPE and slow down its mobility to prevent space charge formation. In addition, this unique asymmetric membrane with a channel upper layer greatly enhances the mobility of Li+ in the GPE due to its low tortuosity and high porosity. The synergistic effect of the ion-dipole interaction and asymmetric structure increases the Li+ transference number to 0.66 and ionic conductivity to 3.36 mS cm−1 (20 °C). Using this superior asymmetric GPE, Li|Li symmetric cells show more stable cycle performance than those using a liquid electrolyte. Li|LiFePO4 batteries with the asymmetric GPE also deliver an impressive electrochemical performance, i.e., coulombic efficiency of 99.5% at 2C after 600 cycles. In consequence, this novel asymmetric GPE possesses potential application in high energy LMBs.

Caesium silver bismuth halide double perovskites, in the first instance Cs2AgBiBr6, were recently introduced to the field of emerging photovoltaics as environmentally friendly, non-toxic and thermodynamically stable photoabsorber materials. However, the wide indirect bandgaps of these materials indicate the need for bandgap engineering and enhancing the light absorption to improve the photovoltaic performance. The present work demonstrates that this can be achieved via modification of the double perovskite with sulphide to obtain caesium silver bismuth sulphobromide materials, Cs2AgBiBr6−2xSx, which have been synthesised as pin-hole-free uniform films and systematically investigated herein. Notable enhancements in the intrinsic light absorption for 0 ≤ x ≤ 0.2 are demonstrated, as are the improvements by up to 50% in the photocurrent density of the corresponding thin-film solar cells. The devices based on the films with the nominal composition Cs2AgBiBr5.8S0.1 delivered a short-circuit current density of 3.0 ± 0.3 mA cm−2 and a power conversion efficiency of 1.9 ± 0.1% (cf. 2.1 ± 0.2 mA cm−2 and 1.3 ± 0.1%, respectively, for the control cells based on the sulphide-free Cs2AgBiBr6). Equally important, caesium silver bismuth sulphobromides demonstrate excellent stability against all common environmental stimuli, viz. heat, light, and humidity.

Magnesium halide salts are an exciting prospect as stable and high-performance electrolytes for rechargeable Mg batteries (RMBs). By nature of their complex equilibria, these salts exist in solutio...

Designing new nanoporous materials with high methane delivery capacity (DC) is crucial to achieve US Department of Energy (DOE) targets of 315 v/v and 0.5 g/g for the transportation applications. We have performed extensive computational studies of methane adsorption in around 9000 multilayer frameworks (MFs) to achieve these targets. Our analysis shows that close placement of methane binding sites, optimum range of framework interaction, and pore size give rise to high methane DC in nanoporous materials. We found the highest DC of 319 v/v in general multilayer frameworks (GMFs) at 298 K. Further, we probed MFs made of graphene sheets and observed high DC of 297 v/v and 0.42 g/g in MFs with 11 and 20 A of interlayer separation, respectively. These values are close to DOE target; however, experimental realization of such MFs is difficult. Therefore, we explored methane adsorption in experimentally feasible pillared graphene frameworks (PGFs) where graphene layers are stacked with the help of suitable linker. Among the various linkers probed, PGF with cubane linker has significantly higher uptake and DC of 317 and 261 v/v, respectively. Further, we observed that in these frameworks changing adsorption and desorption temperature attains DOE target at lower pressures.

Developing an electrolyte candidate with a wide voltage window, highly reversible cycling with Mg-metal anode, and without the use of any flammable solvents is a major challenge for rechargeable Mg...

Quantum dots (QD) with electric-field-controlled charge state are promising for electronics applications, e.g., digital information storage, single-electron transistors, and quantum computing. Inor...

The γ ' ( Ag 2 Al ) phase in the Al–Ag alloy system has served as a textbook example for understanding phase transformations, precipitating hexagonal close-packed (HCP) crystals in the face-centred cubic (FCC) aluminium matrix. The γ ' precipitates display fully coherent interfaces at their broad facets and semicoherent interfaces at their edges. Shockley partial dislocations are expected to decorate the semicoherent interface due to the FCC-HCP structural transformation. Determining the exact locations and core structures of interfacial dislocations, however, remains challenging. In this study, we used aberration-corrected scanning transmission electron microscopy and atomistic simulations to re-visit this classical system. We characterised and explained the Ag segregation at coherent interfaces in the early stage of precipitation. For semicoherent interfaces, interfacial dislocations and reconstructions were revealed by bridging advanced microstructure characterisation and atomistic simulations. In particular, we discovered a new FCC/HCP interfacial structure that displays a unique combination of Shockley partial, Lomer-Cottrell and Hirth dislocations that evolve from the known interfacial structure purely composed by Shockley partial dislocations. Our findings show that the FCC-HCP transformation is more complex than hitherto considered, due to the interplay between structure and composition confined at interfaces.

Intrinsic magnetic topological insulators offer low disorder and large magnetic band gaps for robust magnetic topological phases operating at higher temperatures. By controlling the layer thickness, emergent phenomena such as the quantum anomalous Hall (QAH) effect and axion insulator phases have been realized. These observations occur at temperatures significantly lower than the Néel temperature of bulk MnBi

The kagome lattice, whose electronic valence band (VB) structure includes two Dirac bands and one flat band, offers a rich space to realise tuneable topological and strongly correlated electronic phases in two-dimensional (2D) and layered materials. While strong electron correlations have been observed in inorganic kagome crystals, they remain elusive in organic systems. The latter offer versatile synthesis protocols via molecular self-assembly and metal-ligand coordination. Here, we report the synthesis of a 2D metal-organic framework (MOF) where di-cyano-anthracene (DCA) molecules form a kagome arrangement via coordination with copper (Cu) atoms on a silver surface [Ag(111)]. Low-temperature scanning tunnelling spectroscopy revealed Kondo screening--by the Ag(111) conduction electrons--of magnetic moments localised at Cu and DCA sites of the MOF. Density functional theory and mean-field Hubbard modelling show that these local moments emerge from strong interactions between kagome MOF electrons, enabling organic 2D materials as viable platforms for strongly correlated nanoelectronics and spintronics., Main text: 32 pages, 5 figures. Supplementary Information: 51 pages, 20 figures

Accurate modelling of intracellular calcium ion ( $$Ca^{2+}$$ ) concentration evolution is valuable as it is known to rapidly increase during a Traumatic Brain Injury. In the work presented here, our older non-spatial model dealing with the effect of mechanical stress upon the $$Ca^{2+}$$ transportation in a neuron is spatialized by considering the brain tissue as a solid continuum with the $$Ca^{2+}$$ activity occurring at every material point. Starting with one-dimensional representation, the brain tissue geometry is progressively made realistic and under the action of pressure or kinematic impulses, the effect of dimensionality and material behaviour on the correlation between the stress and concomitant $$Ca^{2+}$$ concentration is investigated. The spatial calcium kinetics model faithfully captures the experimental observations concerning the $$Ca^{2+}$$ concentration, load rate, magnitude and duration and most importantly shows that the critical location for primary injury may not be the most important location as far as secondary injury is concerned.

With its monoelemental composition, various crystalline forms and an inherently strong spin-orbit coupling, bismuth has been regarded as an ideal prototype material to expand our understanding of topological electronic structures. In particular, two-dimensional bismuth thin films have attracted a growing interest due to potential applications in topological transistors and spintronics. This calls for an effective physical model to give an accurate interpretation of the novel topological phenomena shown by two-dimensional bismuth. However, the conventional semi-empirical approach of adapting bulk bismuth hoppings fails to capture the topological features of two-dimensional bismuth allotropes because the electronic band topology is heavily influenced by crystalline symmetries as well as atom spacings. Here we provide a new parameterization using localized Wannier functions derived from the Bloch states in first-principles calculations. We construct new tight-binding models for three types of two-dimensional bismuth allotropes: a Bi (111) bilayer, bismuthene and a Bi(110) bilayer. We demonstrate that our tight-binding models can successfully reproduce the band structures, symmetries and topological features of these two-dimensional allotropes. We anticipate that these models can be extended to other similar two-dimensional topological structures such as antimonene and arsenene. Moreover, these models can serve as a starting point for investigating the electron/spin transport and electromagnetic response in low-dimensional topological devices., 20 pages, 6 figures

The extensive use of halomethanes (CH3X, X = F, Cl, Br, I) as refrigerants, propellants, and pesticides has drawn serious concern due to their adverse biological and atmospheric impact. However, there are currently no portable rapid and accurate monitoring systems for their detection. This work introduces an approach for the selective and sensitive detection of halomethanes using photoluminescence spectral shifts in cesium lead halide perovskite nanocrystals. Focusing on iodomethane (CH3I) as a model system, it is shown that cesium lead bromide (CsPbBr3) nanocrystals can undergo rapid (

Layered two-dimensional van der Waals (vdW) semiconductors and their heterostructures have been shown to exhibit positive photoconductance (PPC) in many studies. A few recent reports have demonstrated negative photoconductance (NPC) as well that can enable broadband photodetection besides multi-level optoelectronic logic and memory. Controllable and reversible switching between PPC and NPC is a key requirement for these applications. This report demonstrates visible-to-near infrared wavelength-driven NPC and PPC, along with reversible switching between the two, in an air stable, high mobility, broadband black phosphorus (BP) field effect transistor (FET) covered with a few layer MoS$_2$ flake. The crossover switching wavelength can be tuned by varying the MoS$_2$ bandgap through its flake thickness and the NPC and PPC photoresponsivities can be modulated using electrostatic gating as well as laser power. Recombination-driven NPC and PPC allows for reversible switching at reasonable time scales of a few seconds. Further, gate voltage-dependent negative persistent photoconductance enables synaptic behavior that is well-suited for optosynaptic applications., Comment: Main Manuscript and Supporting Information

Accurate modelling of intracellular calcium ion ([Formula: see text]) concentration evolution is valuable as it is known to rapidly increase during a Traumatic Brain Injury. In the work presented here, our older non-spatial model dealing with the effect of mechanical stress upon the [Formula: see text] transportation in a neuron is spatialized by considering the brain tissue as a solid continuum with the [Formula: see text] activity occurring at every material point. Starting with one-dimensional representation, the brain tissue geometry is progressively made realistic and under the action of pressure or kinematic impulses, the effect of dimensionality and material behaviour on the correlation between the stress and concomitant [Formula: see text] concentration is investigated. The spatial calcium kinetics model faithfully captures the experimental observations concerning the [Formula: see text] concentration, load rate, magnitude and duration and most importantly shows that the critical location for primary injury may not be the most important location as far as secondary injury is concerned.

In this study, first-principles density functional theory (DFT) calculations are performed to investigate the contribution of each individual reaction at the magnesium/water interface. Thermodynamic and kinetic models derived from the DFT-calculated parameters are used to describe interdependent reactions at the interface and the resultant magnesium electrochemical activity at different pH and potentials. These models are able to rationalise experimental findings, such as those obtained from polarisation and immersion tests, and provide new insights for defining a complete and viable mechanism of aqueous magnesium electrochemistry.

We use angle-resolved photoemission spectroscopy to investigate the electronic structure of bilayer graphene at high n-doping and extreme displacement fields, created by intercalating epitaxial monolayer graphene on silicon carbide with magnesium to form quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide. Angle-resolved photoemission spectroscopy reveals that upon magnesium intercalation, the single massless Dirac band of epitaxial monolayer graphene is transformed into the characteristic massive double-band Dirac spectrum of quasi-freestanding bilayer graphene. Analysis of the spectrum using a simple tight binding model indicates that magnesium intercalation results in an n-type doping of 2.1 $\times$ 10$^{14}$ cm$^{-2}$, creates an extremely high displacement field of 2.6 V/nm, opening a considerable gap of 0.36 eV at the Dirac point. This is further confirmed by density-functional theory calculations for quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide, which show a similar doping level, displacement field and bandgap. Finally, magnesium-intercalated samples are surprisingly robust to ambient conditions; no significant changes in the electronic structure are observed after 30 minutes exposure in air., 46 pages including supporting information, 4 figures in the main paper and 9 figures in the supporting information

Molybdenum based compounds are an emerging class of non-metallic catalytic materials for the hydrogen evolution reaction (HER) in acidic media. However, most of them lose considerable catalytic performance and exhibit poor long-term stability in alkaline media. Here, planar molybdenum oxide, with high alkaline stability and ordered intracrystalline pores, is developed as the HER candidate. The pores with diameters in the order of ∼5–7 A are HER-active, and appear after an NH4+ doping-driven phase transition from the orthorhombic to hexagonal phase. Such a unique structure facilitates the diffusion of ionic entities and water molecules to the HER sites and helps in the removal of gaseous products, therefore improving the surface active area and reaction kinetics. These intracrystalline pores also reduce the long term stress on electrodes. The corresponding HER activity is extremely stable for >40 h in an alkaline medium at an overpotential of 138 mV with a Tafel slope of 50 mV dec−1. Such properties offer a superior combination compared to those of other reported molybdenum based nanostructures, hence providing a great opportunity for developing high-performance alkaline non-metal HER catalysts.

Controlling the semiconductor nanoparticles (NPs) size can alter their optical and electronic properties, which is an important feature for many optoelectronic device applications. In this study, we demonstrated a simple and economical approach to synthesize size-controlled Cu2ZnSnS4 (CZTS) NPs and their application as an absorber layer in solar cells. The size of the CZTS NPs has been controlled from 2.5 to 8 ( ± 0.5) nm by variation of the amine to the precursor mole ratio. The impact of the particle size on the structural, optical, and electrical performance of the devices are studied systematically. XRD and Raman spectroscopy measurements reveal the formation of pure kesterite phase of the CZTS. Moreover, the UV–vis spectroscopy data show that the CZTS NP films have a high optical absorption coefficient (104 cm−1) in the visible region, and its optical band gap is in the range of 1.50–1.62 eV. The power conversion efficiency of a solar cell fabricated using CZTS NPs is enhanced considerably from 3.6% to 4.8% with an increase of nanoparticles size, within an active area of 1.0 ± 0.1 cm2. The maximum external quantum efficiency of 59% is obtained for the solar cell with CZTS thin film comprising 8 nm particles. The observed changes in the device performance parameters might be due to the variation of the thin film microstructure.

The application of ultrathin two-dimensional (2D) perovskites in near-infrared and visible-range optoelectronics has been limited owing to their inherent wide bandgaps, large excitonic binding energies and low optical absorption at higher wavelengths. Here, we show that by tailoring interfacial band alignments via conjugation with low-dimensional materials like monolayer transition metal dichalcogenides (TMD), the functionalities of 2D perovskites can be extended to diverse, visible-range photophysical applications. Based on the choice of individual constituents in the 2D perovskite/TMD heterostructures, our first principles calculations demonstrate widely tunable type-II band gaps, carrier effective masses and band offsets to enable an effective separation of photogenerated excitons for enhanced photodetection and photovoltaic applications. In addition, we show the possibilities of achieving a type-I band alignment for recombination based light emitters as well as a type-III configuration for tunnelling devices. Further, we evaluate the effect of strain on the electronic properties of the heterostructures to show a significant strain tolerance, making them prospective candidates in flexible photosensors., Comment: 38 pages, main manuscript and supporting information

Crack closure, the contact between opposing crack faces above zero load, has traditionally been used to explain the observation that higher stress ratio fatigue cycles have faster growth rates than lower stress ratio cycles. Using new techniques to investigate the dependance of stress ratio on crack closure, we tested simplified variable amplitude loading sequences containing segments of 100 cycles at different stress ratios in AA7050-T7451 alloy. We compared the crack growth at different stress ratios at the start of a coupon with no closure and after 5 mm or more of crack growth where significant closure had developed as indicated by side and back-face strain gauges mounted on the coupon. Fractographic measurements of the fatigue growth from these sequences show the same stress ratio effect at the start of loading and after 5 mm of growth, suggesting that the stress ratio effect occurs soon after the commencement of growth and that crack closure is not the dominant cause of the stress ratio effect in the AA7050-T7451 alloy. Results from these tests using constant and varying maximum stress intensity K max also showed significantly different stress ratio effects. Traditional constant amplitude load tests over-predict the rate of crack growth for cycles in which the maximum load is varying. Obtaining crack growth rates for a range of different stress ratios from variable amplitude testing in this way can allow greater accuracy to be achieved in predicting the rate of crack growth for arbitrary variable amplitude loading sequences.

Supramolecular chemistry protocols applied on surfaces offer compelling avenues for atomic-scale control over organic-inorganic interface structures. In this approach, adsorbate-surface interactions and two-dimensional confinement can lead to morphologies and properties that differ dramatically from those achieved via conventional synthetic approaches. Here, we describe the bottom-up, on-surface synthesis of one-dimensional coordination nanostructures based on an iron (Fe)-terpyridine (tpy) interaction borrowed from functional metal-organic complexes used in photovoltaic and catalytic applications. Thermally activated diffusion of sequentially deposited ligands and metal atoms and intraligand conformational changes lead to Fe-tpy coordination and formation of these nanochains. We used low-temperature scanning tunneling microscopy and density functional theory to elucidate the atomic-scale morphology of the system, suggesting a linear tri-Fe linkage between facing, coplanar tpy groups. Scanning tunneling spectroscopy reveals the highest occupied orbitals, with dominant contributions from states located at the Fe node, and ligand states that mostly contribute to the lowest unoccupied orbitals. This electronic structure yields potential for hosting photoinduced metal-to-ligand charge transfer in the visible/near-infrared. The formation of this unusual tpy/tri-Fe/tpy coordination motif has not been observed for wet chemistry synthetic methods and is mediated by the bottom-up on-surface approach used here, offering pathways to engineer the optoelectronic properties and reactivity of metal-organic nanostructures.

A high sensitive glucose sensing characteristic has been realized in carbon nano-onions (CNOs). The CNOs of mean size 30 nm were synthesized by an energy-efficient, simple and inexpensive combustion technique. These as-synthesized CNOs could be employed as an electrochemical sensor by covalently immobilizing the glucose oxidase enzyme on them via carbodiimide chemistry. The sensitivity achieved by such a sensor is 26.5 µA mM−1 cm−2 with a linear response in the range of 1–10 mM glucose. Further to improve the catalytic activity of the CNOs and also to make them enzyme free, platinum nanoparticles of average size 2.5 nm are decorated on CNOs. This sensor fabricated using Pt-decorated CNOs (Pt@CNOs) nanostructure has shown an enhanced sensitivity of 21.6 µA mM−1 cm−2 with an extended linear response in the range of 2–28 mM glucose. Through these attempts we demonstrate CNOs as a versatile biosensing platform.

Understanding atomic-level mechanisms of methane adsorption in nanoporous materials is of great importance to increase their methane storage capacity targeting energy sources with low carbon emission. In this work, we considered layered covalent organic frameworks (COFs) with low density and revealed the effect of slipping and chemical functionalization on their methane adsorption and separation properties. We performed grand canonical Monte Carlo simulations studies of methane (CH4) adsorption and carbon-dioxide:methane (CO2:CH4) separation in various slipped structures of TpPa1, TpBD, PI-COFs, and functionalized TpPa1 and TpBD COFs as well. We observed that the slipping improves the total CH4 uptake by 1.1–1.5 times, while functionalization does not have a significant effect on CH4 uptake. We also observed improvement in CO2:CH4 selectivity due to slipping, whereas functionalization results in decrease in the selectivity. In all considered COFs, we found the highest CH4 delivery capacity of 141 cm3 (STP...

Non-covalent functionalization of graphene materials with responsive polymers is a promising approach for synthesizing new, hybrid composites with improved dispersibility and functional properties. However, the interplay between various components of the hybrid systems, their structural configurations, and stimuli-responsive behavior are not yet well understood at the atomic level. Here, we investigate the temperature-responsive behavior of physisorbed poly(N-isopropylacrylamide) (PNIPAM) on to graphene (G) and graphene oxide (GO) sheets in aqueous solution using large scale molecular dynamics simulations. It was observed that PNIPAM can be spontaneously anchored to the surfaces of both G and GO at 290 K with a macromolecular coil shape. However, the configuration of PNIPAM on G is markedly different in comparison with that on GO, leading to its distinct thermoresponsive behavior. Specifically, the adsorption on G gives rise to an increase in the temperature of the coil-to-globule transition when compared to the native polymer, the origin of which can be interpreted in terms of the interactions and the solvation behavior. The results obtained here are of significance to the design and manipulation of graphene-based stimuli-responsive hybrid systems with optimal functional properties.

Microalloying is a routine method to optimize precipitation and mechanical properties in light metals. Here we study how In and Sb (0.025 at.%) additions in an Al-1.7 at.% Cu alloy benefit precipitation during ageing and investigate the underlying mechanism using scanning transmission electron microscopy and density functional theory (DFT) calculations. The combined additions accelerate precipitation kinetics and increase peak hardness through two different ways. In samples aged directly at low temperatures (≤200 °C) after solid solution treatment, cubic close-packed InSb nanocrystals form first. The truncated {002} surfaces of InSb particles induce the preferential nucleation of Guinier-Preston (GP) zones, θ″ and θ′ successively. However, in samples aged at 250 °C, precipitation of θ′ precedes that of InSb particles. Supersaturated vacancies trapped by In and Sb solute atoms/clusters play a critical role in switching the precipitation sequence. By tuning how strong the binding between a vacancy and solute atoms is, we successfully invert the temperature dependence of the precipitation sequence. These findings will contribute to understanding precipitation mechanisms and optimizing precipitate distribution in aluminium precipitation hardenable alloys.

The edge states are of particular importance to understand fundamental properties of finite two-dimensional (2D) crystals. Based on first-principles calculations, we investigated on the bare zigzag boron nitride nanoribbons (zzBNNRs) with different spin-polarized states well localized at and extended along their edges. Our calculations examined the edge stress, which is sensitively dependent on the magnetic edge states, for either B-terminated edge or N-terminated edge. Moreover, we revealed that different magnetic configurations lead to a rich spectrum of electronic behaviors at edges. Using an uniaxial tensile strain, we proposed the magnetic phase transitions and thereby obtained the metallic to half-metallic (or reverse) phase transitions at edges. It suggests zzBNNR as a promising candidate for potential applications of non-metal spintronic devices.

The emergence of graphene in recent years provides exciting avenues for achieving fast, reliable DNA/RNA sensing and sequencing. Here we explore the possibility of enhancing electronic fingerprints of nucleobases adsorbed on graphene by tuning the surface coverage and modifying molecular dipoles using first-principles calculations. We demonstrate that intermolecular interactions have a strong influence on the adsorption geometry and the electronic structure of the nucleobases, resulting in tilted configurations and a considerable modification of their electronic fingerprints in graphene. Our analysis reveals that the molecular dipole of the nucleobase molecules plays a dominant role in the electronic structure of graphene-nucleobase systems, inducing significant changes in the work functions and energy level alignments at the interface. These results highlight tunable control of the measured molecular signals in graphene by optimizing the surface contact between nucleobases and graphene. Our findings have important implications for identification and understanding of molecular fingerprints of DNA/RNA nucleobases in graphene-based sensing and sequencing methods.

Pn heterojunctions comprising layered van der Waals (vdW) semiconductors have been used to demonstrate current-rectifiers, photodetectors, and photovoltaic devices. However, a direct or near-direct heterointerface bandgap for enhanced photogeneration in high light-absorbing few-layer vdW materials remains unexplored. In this work, for the first time, density functional theory calculations show that the heterointerface of few-layer group-6 transition metal dichalcogenide (TMD) WSe

Phonon polaritons (PhPs) have attracted significant interest in the nano-optics communities because of their nanoscale confinement and long lifetimes. Although PhP modification by changing the local dielectric environment has been reported, controlled manipulation of PhPs by direct modification of the polaritonic material itself has remained elusive. Here, chemical switching of PhPs in α-MoO3 is achieved by engineering the α-MoO3 crystal through hydrogen intercalation. The intercalation process is non-volatile and recoverable, allowing reversible switching of PhPs while maintaining the long lifetimes. Precise control of the intercalation parameters enables analysis of the intermediate states, in which the needle-like hydrogenated nanostructures functioning as in-plane antennas effectively reflect and launch PhPs and form well-aligned cavities. We further achieve spatially controlled switching of PhPs in selective regions, leading to in-plane heterostructures with various geometries. The intercalation strategy introduced here opens a relatively non-destructive avenue connecting infrared nanophotonics, reconfigurable flat metasurfaces and van der Waals crystals., G.Á.-P. acknowledges support through the Severo Ochoa Program from the Government of the Principality of Asturias (PA20-PF-BP19-053). P.A.-G. and J.D. acknowledge support from the European Research Council under starting grant no. 715496, 2DNANOPTICA. Q.B. acknowledges support from the Australian Research Council (ARC, FT150100450 and IH150100006). Q.B. and Q.O. acknowledge support from the Australian Research Council Centre of Excellence in Future Low-Energy Electronics Technologies (FLEET) (project number: CE170100039).

The intercalation of epitaxial graphene on SiC(0001) with Ca has been studied extensively, yet precisely where the Ca resides remains elusive. Furthermore, the intercalation of Mg underneath epitaxial graphene on SiC(0001) has not been reported. Here, we use low energy electron diffraction, x-ray photoelectron spectroscopy, secondary electron cut-off photoemission and scanning tunneling microscopy to elucidate the physical and electronic structure of both Ca- and Mg-intercalated epitaxial graphene on 6H-SiC(0001). We find that Ca intercalates underneath the buffer layer and bonds to the Si-terminated SiC surface, breaking the C-Si bonds of the buffer layer i.e. 'freestanding' the buffer layer to form Ca-intercalated quasi-freestanding bilayer graphene (Ca-QFSBLG). The situation is similar for the Mg-intercalation of epitaxial graphene on SiC(0001), where an ordered Mg-terminated reconstruction at the SiC surface and Mg bonds to the Si-terminated SiC surface are formed, resulting in Mg-intercalated quasi-freestanding bilayer graphene (Mg-QFSBLG). Ca-intercalation underneath the buffer layer has not been considered in previous studies of Ca-intercalated epitaxial graphene. Furthermore, we find no evidence that either Ca or Mg intercalates between graphene layers. However, we do find that both Ca-QFSBLG and Mg-QFSBLG exhibit very low workfunctions of 3.68 and 3.78 eV, respectively, indicating high n-type doping. Upon exposure to ambient conditions, we find Ca-QFSBLG degrades rapidly, whereas Mg-QFSBLG remains remarkably stable., 58 pages, 10 figures, 4 tables. Revised text and figures