Monolayer Square Research Articles

The performance of OPC and OPC3 water models in predictions of 2D structures under nanoconfinement.

Nanoconfined water plays an important role in broad fields of science and engineering. Classical molecular dynamics (MD) simulations have been widely used to investigate water phases under nanoconfinement. The key ingredient of MD is the force field. In this study, we systematically investigated the performance of a recently introduced family of globally optimal water models, OPC and OPC3, and TIP4P/2005 in describing nanoconfined two-dimensional (2D) water ice. Our studies show that the melting points of the monolayer square ice (MSI) of all three water models are higher than the melting points of the corresponding bulk ice Ih. Under the same conditions, the melting points of MSI of OPC and TIP4P/2005 are the same and are ∼90K lower than that of the OPC3 water model. In addition, we show that OPC and TIP4P/2005 water models are able to form a bilayer AA-stacked structure and a trilayer AAA-stacked structure, which are not the cases for the OPC3 model. Considering the available experimental data and first-principles simulations, we consider the OPC water model as a potential water model for 2D water ice MD studies.

Strain tunable intrinsic ferromagnetic in 2D square CrBr2

Two-dimensional intrinsic magnetic materials with high Curie temperature (Tc) coexisting with 100% spin polarization are highly desirable for realizing promising spintronic devices. In the present work, the intrinsic magnetism of monolayer square CrBr2 is predicted by using first-principles calculations. The monolayer CrBr2 is an intrinsic ferromagnetic half-metal with the half-metallic gap of 1.58 eV. Monte Carlo simulations based on the Heisenberg model estimate Tc as 212 K. Furthermore, the large compressive strain makes CrBr2 undergo ferromagnetic–antiferromagnetic phase transition when the biaxial tensile strain larger than 9.3% leads to the emergence of semiconducting electronic structures. Our results show that the intrinsic half-metal with a high Tc and controllable magnetic properties endow monolayer square CrBr2 as a potential material for spintronic applications.

D-SEAMS: Deferred Structural Elucidation Analysis for Molecular Simulations.

Structural analyses are an integral part of computational research on nucleation and supercooled water, whose accuracy and efficiency can impact the validity and feasibility of such studies. The underlying molecular mechanisms of these often elusive and computationally expensive processes can be inferred from the evolution of ice-like structures, determined using appropriate structural analysis techniques. We present d-SEAMS, a free and open-source postprocessing engine for the analysis of molecular dynamics trajectories, which is specifically able to qualitatively classify ice structures in both strong-confinement and bulk systems. For the first time, recent algorithms for confined ice structure determination have been implemented, along with topological network criteria for bulk ice structure determination. We also propose and validate a new order parameter for identifying the building blocks of quasi-one-dimensional ice. Recognizing the need for customization in structural analysis, d-SEAMS has a unique code architecture built with nix and employing a YAML-Lua scripting pipeline. The software has been designed to be user-friendly and extensible. The engine outputs are compatible with popular graphics software suites, allowing for immediate visual insights into the systems studied. We demonstrate the features of d-SEAMS by using it to analyze nucleation in the bulk regime and for quasi-one- and quasi-two-dimensional systems. Structural time evolution and quantitative metrics are determined for heterogeneous ice nucleation on a silver-exposed β-AgI surface, homogeneous ice nucleation, flat monolayer square ice formation, and freezing of an ice nanotube.

Phase behaviors of deeply supercooled bilayer water unseen in bulk water

Akin to bulk water, water confined to an isolated nanoslit can show a wealth of new 2D phases of ice and amorphous ice, as well as unusual phase behavior. Indeed, 2D water phases, such as bilayer hexagonal ice and monolayer square ice, have been detected in the laboratory, confirming earlier computational predictions. Herein, we report theoretical evidence of a hitherto unreported state, namely, bilayer very low density amorphous ice (BL-VLDA), as well as evidence of a strong first-order transition between BL-VLDA and the BL amorphous ice (BL-A), and a weak first-order transition between BL-VLDA and the BL very low density liquid (BL-VLDL) water. The diffusivity of BL-VLDA is typically in the range of 10-9 cm2/s to 10-10 cm2/s. Similar to bulk (3D) water, 2D water can exhibit two forms of liquid in the deeply supercooled state. However, unlike supercooled bulk water, for which the two forms of liquid can coexist and merge into one at a critical point, the 2D BL-VLDL and BL high-density liquid (BL-HDL) phases are separated by the highly stable solid phase of BL-A whose melting line exhibits the isochore end point (IEP) near 220 K in the temperature-pressure diagram. Above the IEP temperature, BL-VLDL and BL-HDL are indistinguishable. At negative pressures, the metastable BL-VLDL exhibits a spatially and temporally heterogeneous structure induced by dynamic changes in the nanodomains, a feature much less pronounced in the BL-HDL.

Structural and dynamic characteristics in monolayer square ice.

When water is constrained between two sheets of graphene, it becomes an intriguing monolayer solid with a square pattern due to the ultrahigh van der Waals pressure. However, the square ice phase has become a matter of debate due to the insufficient experimental interpretation and the slightly rhomboidal feature in simulated monolayer square-like structures. Here, we performed classical molecular dynamics simulations to reveal monolayer square ice in graphene nanocapillaries from the perspective of structure and dynamic characteristics. Monolayer square-like ice (instantaneous snapshot), assembled square-rhombic units with stacking faults, is a long-range ordered structure, in which the square and rhombic units are assembled in an order of alternative distribution, and the other rhombic unit forms stacking faults (polarized water chains). Spontaneous flipping of water molecules in monolayer square-like ice is intrinsic and induces transformations among different elementary units, resulting in the structural evolution of monolayer square ice in dynamics. The existence of stacking faults should be attributed to the spontaneous flipping behavior of water molecules under ambient temperature. Statistical averaging results (thermal average positions) demonstrate the inherent square characteristic of monolayer square ice. The simulated data and insight obtained here might be significant for understanding the topological structure and dynamic behavior of monolayer square ice.

Growth of Single-Crystalline Cadmium Iodide Nanoplates, CdI2/MoS2 (WS2, WSe2) van der Waals Heterostructures, and Patterned Arrays.

Two-dimensional layered materials (2DLMs) have attracted considerable recent interest for their layer-number-dependent physical and chemical properties, as well as potential technological opportunities. Here we report the synthesis of two-dimensional layered cadmium iodide (CdI2) nanoplates using a vapor transport and deposition approach. Optical microscopy and scanning electron microscopy studies show that the resulting CdI2 nanoplates predominantly adopt hexagonal and triangular morphologies with a lateral dimension of ∼2-10 μm. Atomic force microscopy studies show that the resulting nanoplates exhibit a thickness in the range of 5-220 nm with a relatively smooth surface. X-ray diffraction studies reveal highly crystalline CdI2 in hexagonal phase, which is also confirmed by the characteristic Raman Ag mode at 110 cm-1. High-resolution transmission electron microscopy and selected area electron diffraction reveal that the resulting CdI2 nanoplates are single crystals. Taking a step further, we show the CdI2 nanoplates were readily grown on other 2DLMs (e.g., WS2, WSe2, MoS2), forming diverse van der Waals heterostructures. Using prepatterned WS2 monolayer square arrays as the nucleation and growth templates, we also show that regular arrays of CdI2/WS2 vertical heterostructures can be prepared. The synthesis of the CdI2 nanoplates, heterostructures, and heterostructure arrays offers a valuable material system for 2D materials science and technology.

Lateral topological crystalline insulator heterostructure

The emergence of lateral heterostructures fabricated by two-dimensional building blocks brings many exciting realms in material science and device physics. Enriching available nanomaterials for creating such heterostructures and enabling the underlying new physics is highly coveted for the integration of next-generation devices. Here, we report a breakthrough in lateral heterostructure based on the monolayer square transition-metal dichalcogenides MX2 (M = W, X = S/Se) modules. Our results reveal that the MX2 lateral heterostructure (1S-MX2 LHS) can possess excellent thermal and dynamical stability. Remarkably, the highly desired two-dimensional topological crystalline insulator phase is confirmed by the calculated mirror Chern number . A nontrivial band gap of 65 meV is obtained with SOC, indicating the potential for room-temperature observation and applications. The topologically protected edge states emerge at the edges of two different nanoribbons between the bulk band gap, which is consistent with the mirror Chern number. In addition, a strain-induced topological phase transition in 1S-MX2 LHS is also revealed, endowing the potential utilities in electronics and spintronics. Our predictions not only introduce new member and vitality into the studies of lateral heterostructures, but also highlight the promise of lateral heterostructure as appealing topological crystalline insulator platforms with excellent stability for future devices.

Effects of external magnetic field and magnetic anisotropy on chiral spin structures of square nanodisks investigated with a quantum simulation approach

We employed a quantum simulation approach to investigate the magnetic properties of monolayer square nanodisks with Dzyaloshinsky-Moriya (DM) interaction. The computational program converged very quickly, and generated chiral spin structures on the disk planes with good symmetry. When the DM interaction is sufficiently strong, multi-domain structures appears, their sizes or average distance between each pair of domains can be approximately described by a modified grid theory. We further found that the external magnetic field and uniaxial magnetic anisotropy both normal to the disk plane lead to reductions of the total free energy and total energy of the nanosystems, thus are able to stabilize and/or induce the vortical structures, however, the chirality of the vortex is still determined by the sign of the DM interaction parameter. Moreover, the geometric shape of the nanodisk affects the spin configuration on the disk plane as well.

Quantum spin Hall effect and topological phase transition in two-dimensional square transition-metal dichalcogenides

Two-dimensional (2D) topological insulators (TIs) hold promise for applications in spintronics based on the fact that the propagation direction of edge electrons of a 2D TI is robustly linked to their spin origination. Here, with the use of first-principles calculations, we predict a family of robust 2D TIs in monolayer square transition metal dichalcogenides (MoS2, MoSe2, MoTe2, WS2, WSe2, and WTe2). Sizeable intrinsic nontrivial bulk band gaps ranging from 24 to 187 meV are obtained, guarantying the quantum spin Hall (QSH) effect observable at room temperature in these new 2D TIs. Significantly different from most known 2D TIs with comparable band gaps, these sizeable energy gaps originate from the strong spin-orbit interaction related to the pure d electrons of the Mo/W atoms around the Fermi level. A single pair of topologically protected helical edge states is established for the edge of these systems with the Dirac point locating in the middle of the bulk band gap, and their topologically nontrivial states are also confirmed with nontrivial topological invariant Z2 = 1. More interestingly, by controlling the applied strain, a topological quantum phase transition between a QSH phase and a metallic phase or a trivial insulating phase can be realized in these 2D materials, and the detailed topological phase diagram is established.

Entangled Spin-Orbital Phases in the d9Model

We investigate the phase diagrams of the spin-orbital $d^9$ Kugel-Khomskii model for a bilayer and a monolayer square lattice using Bethe-Peierls-Weiss method. For a bilayer we obtain valence bond phases with interlayer singlets, with alternating planar singlets, and two entangled spin-orbital (ESO) phases, in addition to the antiferromagnetic and ferromagnetic order. Possibility of such entangled phases in a monolayer is under investigation at present.

Fabrication and Light‐Transmission Properties of Monolayer Square Symmetric Colloidal Crystals via Controlled Convective Self‐assembly on 1D Grooves

Self-organization of colloidal spheres within a channel, of which a 1D periodic groove substrate is used as the bottom substrate, is studied. We demonstrate that high-quality monolayer square symmetric colloidal crystals can be achieved only when the colloidal suspension drying front is set parallel to close-packing rows of a commensurate square lattice of the 1D periodic grooves. Experimental optical characterization and theoretical simulations of the samples are presented and discussed.

Control of micro- and nanopatterns of octadecyltrimethoxysilane monolayers using nanoimprint lithography and atmospheric chemical vapor deposition

Octadecyltrimethoxysilane (OTMS) self-assembled monolayers have been grafted on micrometric and nanometric areas of SiO2∕Si substrates using a process combining nanoimprint lithography and atmospheric chemical vapor deposition. The optimization of the process has lead to monolayer square patterns of OTMS with lateral sizes ranging from 2μm down to 50nm. Their coverage uniformity extends on several square millimeters. Their coverage density can be accurately tuned by the deposition time.