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Nanoconfined water plays an indispensable role in various phenomena in biology, chemistry, and engineering. It exhibits many abnormal properties compared to bulk water, especially under strong confinement. However, the origin of those anomalies is still elusive due to the lack of structural information on hydrogen-bonding networks. Considering the inhomogeneity of the nanocavity and the tiny amount of water molecules, conventional optical spectroscopies and nuclear magnetic resonance (NMR) fail to realize the structure analysis of nanoconfined water. Here, we addressed this issue by combining scanning probe microscopy (SPM) with advanced quantum sensing(QS) based on an atomic-size quantum sensor like nitrogen-vacancy (NV) center in diamond, which can apply the nanoscale-NMR for characterizing both the dynamics and structure of confined water at ambient conditions. We built a two-dimensional (2D) nanoconfined water system with a hexagonal-boron nitride (hBN) flake and a hydrophilic diamond surface. By using the SPM tip to measure the confinement size precisely, we observed a critical confinement size of ~2 nm, below which the water diffusion was significantly suppressed and the hydrogen-bonding network of water showed an ordered structure. Meanwhile, molecular dynamics (MD) simulation revealed a solid-like water contact layer on the diamond surface under strong confinement, which also reproduced the measured nanoscale-NMR spectra and confirmed the liquid-solid phase transition observed in the experiments. Notably, with this new SPM-QS platform, our results showed a promising way to elucidate the abnormal properties of nanoconfined water in future applications.

Designing anode materials with high lithium specific capacity is crucial to the development of high energy-density lithium ion batteries. Herein, a distinctive lithium growth mechanism, namely, the restricted multilayered growth for lithium, and a strategy for lithium storage are proposed to achieve the balance between the ultra-high specific capacity and the need to avert uncontrolled dendritic growth of lithium. In particular, based on first-principles computation, we show that the Al2C monolayer with planar tetracoordinate carbon structure can be an ideal platform for realizing the restricted multilayered growth mechanism as a 2D anode material. Furthermore, the Al2C monolayer exhibits ultra-high specific capacity of lithium of 4059 mAh/g, yet with a low dif-fusion barrier of 0.039-0.17 eV as well as low open circuit voltage in the range of 0.002-0.34 V. These novel properties endow the Al2C monolayer a promising anode material for future lithium ion batteries. Our study offers a new way to design promising 2D anode materials with high specific capacity, fast lithium-ion diffusion, and safe lithium storage mechanism.

Silver and copper monohalides can be viewed as a class of compounds in the neutral zone between predominantly covalent and ionic compounds, thereby exhibiting neither strong ionicity nor strong covalency. We show ab initio calculation evidence that silver and copper monohalides entail relatively low transition barriers between the non-polar rock-salt phase and the polar zinc-blende phase, due largely to their unique chemical nature of modest iconicity or covalency. Notably, the low transition barriers endow both monohalides with novel mechanical and electronic properties, i.e., coupled ferroelasticity and ferroelectricity with large polarizations and relatively low switching barriers at ambient conditions. Several halides even possess very similar lattice constants and structures as the prevailing semiconductors such as silicon, thereby enabling epitaxial growth on silicon. Moreover, based on extensive structural search, we find that the most stable two-dimensional (2D) polymorphs of the monolayer halides are close or even greater in energy than their bulk counterparts, a feature not usually seen in the family of rock-salt or zinc-blende semiconductors. The low transition barrier between zinc-blende phase and 2D phase is predicted. Moreover, several 2D monolayer halides also exhibit multiferroicity with coupled ferroelasticity or ferroelectricity, thereby rendering their potential applications as high-density integrated memories for efficient data reading and writing. Their surfaces, covered by halides, also provide oxidation resistance and give low cleave energy from layered structure, suggesting high likelihood of experimental synthesis of these 2D polymorphs.

Two-dimensional (2D) semiconductors with direct and modest bandgap and ultrahigh carrier mobility are highly desired functional materials for nanoelectronic applications. Herein, we predict that monolayer CaP3 is a new 2D functional material that possesses not only a direct bandgap of 1.15 eV (based on HSE06 computation), and also a very high electron mobility up to 19930 cm2 V-1 s-1, comparable to that of monolayer phosphorene. More remarkably, contrary to the bilayer phosphorene which possesses dramatically reduced carrier mobility compared to its monolayer counterpart, CaP3 bilayer possesses even higher electron mobility (22380 cm2 V-1 s-1) than its monolayer counterpart. The bandgap of 2D CaP3 can be tuned over a wide range from 1.15 to 0.37 eV (HSE06 values) through controlling the number of stacked CaP3 layers. Besides novel electronic properties, 2D CaP3 also exhibits optical absorption over the entire visible-light range. The combined novel electronic, charge mobility, and optical properties render 2D CaP3 an exciting functional material for future nanoelectronic and optoelectronic applications.

Exploring giant magnetic anisotropy in small magnetic nanostructures is of both fundamental interest and technological merit for information storage. To prevent spin flipping at room temperature due to thermal fluctuation, large magnetic anisotropy energy (MAE) over 50 meV in magnetic nanostructure is desired for practical applications. We chose one of the smallest magnetic nanostructures-Ir2 dimer, to investigate its magnetic properties and explore possible approach to engineer the magnetic anisotropy. Through systematic first-principles calculations, we found that the Ir2 dimer already possesses giant MAE of 77 meV. We proposed an effective way to enhance the MAE of the Ir2 dimer to 223~294 meV by simply attaching a halogen atom at one end of the Ir-Ir bond. The underlying mechanism for the record high MAE is attributed to the modification of the energy diagram of the Ir2 dimer by the additional halogen-Ir bonding, which alters the spin-orbit coupling Hamiltonian and hence the magnetic anisotropy. Our strategy can be generalized to design other magnetic molecules or clusters with giant magnetic anisotropy.

A grand unified model (GUM) has been proposed recently to understand structure anatomy and evolution of liganded gold clusters. In this work, besidesthe two types of elementary blocks (triangular Au3(2e) and tetrahedral Au4(2e)), we introduce a secondary block, namely, the icosahedral Au13 with 8e valence electrons, noted as Au13(8e). Using this secondary block, structural anatomy and evolution of a special group of liganded gold nanoclusters containing icosahedral Au13 motifs can be conveniently analyzed. In addition, a new ligand-protected cluster Au49(PR3)10(SR)15Cl2 is predicted to exhibit high chemical and thermal stability, suggesting likelihood of its synthesis in the laboratory.

A new two-dimensional (2D) layered material, namely, titanium trisulfide (TiS$_3$) monolayer sheet, is predicted to possess desired electronic properties for nanoelectronic applications. On basis of the first-principles calculations within the framework of density functional theory and deformation theory, we show that the TiS$_3$ 2D crystal is a direct gap semiconductor with a band gap of 1.06 eV and high carrier mobility. More remarkably, the in-plane electron mobility of the 2D TiS$_3$ is highly anisotropic, amounting to $\sim$10,000 cm$^2$V$^{-1}$s$^{-1}$ in the \emph{b} direction, which is higher than that of the MoS$_2$ monolayer. Meanwhile, the hole mobility is about two orders of magnitude lower. We also find that bulk TiS$_3$ possesses lower cleavage energy than graphite, indicating high possibility of exfoliation for TiS$_3$ monolayers or multilayers. Both dynamical and thermal stability of the TiS$_3$ monolayer is examined via phonon-spectrum calculation and Born-Oppenheimer molecular dynamics simulation in \emph{NPT} ensemble. The predicted novel electronic properties render the TiS$_3$ monolayer an attractive 2D material for applications in future nanoelectronics., Comment: 4 figures

We investigate stability and electronic properties of oxy- (=O) or imine- (=NH) functionalized monolayer phosphorene with either single-side or double-side functionalization based on density-functional theory calculations. Our thermodynamic analysis shows that oxy-functionalized phosphorene can be formed under the conditions ranging from ultrahigh vacuum to high concentrations of molecular O2, while the imide-functionalized phosphorene can be formed at relatively high concentration of molecular N2H2. In addition, our Born-Oppenheimer molecular dynamics (BOMD) simulation shows that at the ambient condition both O2 and N2H2 can etch phosphorene away., Comment: appears in RSC Advances, 2014

The supercooled liquid silicon, modeled by Stillinger-Weber potential, shows anomalous increase in heat capacity $C_p$, with a maximum $C_p$ value close to 1060 K at zero pressure. We study equilibration and relaxation of the supercooled SW Si, in the temperature range of 1060 K--1070 K at zero pressure. We find that as the relaxation of the metastable supercooled liquid phase initiates, a straight line region (SLR) is formed in cumulative potential energy distributions. The configurational temperature corresponding to the SLR is close to 1060 K, which was earlier identified as the freezing temperature of 4-coordinated amorphous network. The SLR is found to be tangential to the distribution of the metastable liquid phase and thus influences the broadness of the distribution. As the bath temperature is reduced from 1070 K to 1060 K, the effective temperature approaches the bath temperature which results in broadening of the metastable phase distribution. This, in turn, causes an increase in overall fluctuations of potential energy and hence an increase of heat capacity. We also find that during initial stages of relaxation, 4-coordinated atoms form 6-membered rings with a chair--like structure and other structural units that indicate crystallization. Simultaneously a strong correlation is established between the number of chair-shaped 6-membered rings and the number of 4-coordinated atoms in the system. This shows that all properties related to 4-coordinated particles are highly correlated as the SLR is formed in potential energy distributions and this can be interpreted as a consequence of `freezing' of amorphous network formed by 4-coordinated particles., Comment: Submitted to a Peer-reviewed Journal on 28 January 2014

We perform a comprehensive first-principles study of the electronic properties of phosphorene nanoribbons, phosphorene nanotubes, multilayer phosphorene, and heterobilayers of phosphorene and two-dimensional (2D) transition metal dichalcogenide (TMDC) monolayer. The tensile strain and electric-field effects on electronic properties of low-dimensional phosphorene nanostructures are also investigated. Our calculations show that zigzag phosphorene nanoribbons (z-PNRs) are metals, regardless of the ribbon width while armchair phosphorene nanoribbons (a-PNRs) are semiconductors with indirect bandgaps and the bandgaps are insensitive to variation of the ribbon width. We find that tensile compression (or expansion) strains can reduce (or increase) the bandgap of the a-PNRs while an in-plane electric field can significantly reduce the bandgap of a-PNRs, leading to the semiconductor-to-metal transition beyond certain electric field. For single-walled phosphorene nanotubes (SW-PNTs), both armchair and zigzag nanotubes are semiconductors with direct bandgaps. With either tensile strains or transverse electric field, similar behavior of bandgap modulation can arise as that for a-PNRs. It is known that multilayer phosphorene sheets are semiconductors with their bandgaps decreasing with increasing the number of multilayers. In the presence of a vertical electric field, the bandgaps of multilayer phosphorene sheets decrease with increasing the electric field, and the bandgap modulation is more significant with more layers. Lastly, heterobilayers of phosporene with a TMDC (MoS2 or WS2) monolayer are still semiconductors while their bandgaps can be reduced by applying a vertical electric field as well.

Phosphorene, a monolayer of black phosphorus, is promising for nanoelectronic applications not only because it is a natural p-type semiconductor but also it possesses a layer-number dependent direct bandgap (in the range of 0.3 eV~1.5 eV). On basis of the density functional theory calculations, we investigate electronic properties of the bilayer phosphorene with different stacking orders. We find that the direct bandgap of the bilayers can vary from 0.78 - 1.04 eV with three different stacking orders. In addition, a vertical electric field can further reduce the bandgap down to 0.56 eV (at the field strength 0.5 V/{\AA}). More importantly, we find that when a monolayer of MoS_2 is superimposed with the p-type AA- or AB-stacked bilayer phosphorene, the combined tri-layer can be an effective solar-cell material with type-II heterojunction alignment. The power conversion efficiency is predicted to be ~18% or 16% with AA- or AB-stacked bilayer phosphorene, higher than reported efficiencies of the state-of-the-art trilayer graphene/transition metal dichalcogenide solar cells., Comment: Journal of Physical Chemistry Letters, March, 2014

We have performed a systematic first-principles study of the effect of tensile strains on the electronic properties of early transition-metal dichalcogenide (TMDC) monolayers MX2 (M = Sc, Ti, Zr, Hf, Ta, Cr; X = S, Se, and Te). Our density-functional theory (DFT) calculations suggest that the tensile strain can significantly affect the electronic properties of many early TMDCs in general and the electronic bandgap in particular. For group IVB TMDCs (TiX2, ZrX2, HfX2), the bandgap increases with the tensile strain, but for ZrX2 and HfX2 (X=S, Se), the bandgap starts to decrease at strain 6% to 8%. For the group-VB TMDCs (TaX2), the tensile strain can either induce the ferromagnetism or enhance the existing ferromagnetism. For the group-VIB TMDCs (CrX2) the direct-to-indirect bandgap transition is seen upon application of the tensile strain, except CrTe2 whose bandgap decreases with the tensile strain even though the direct character of its bandgap is retained. Lastly, for the group-IIIB TMDCs (ScX2) in the T metallic phase, we find that the tensile strain has little effect on their electronic and magnetic properties. Our study suggests that strain engineering is an effective approach to modify electronic and magnetic properties of most early TMDC monolayers, thereby opening an alternative way for future optoelectronic and spintronic applications., Comment: Journal of Physical Chemistry C, 2014