2D Crystals Research Articles

Energy conservation for the weak solutions to the 3D compressible nematic liquid crystal flow

Energy conservation for the weak solutions to the 3D compressible nematic liquid crystal flow

Toward Controlled Synthesis of 2D Crystals by CVD: Learning from the Real-Time Crystal Morphology Evolutions.

The rich morphology of 2D materials grown through chemical vapor deposition (CVD), is a distinctive feature. However, understanding the complex growth of 2D crystals under practical CVD conditions remains a challenge due to various intertwined factors. Real-time monitoring is crucial to providing essential data and enabling the use of advanced tools like machine learning for unraveling these complexities. In this study, we present a custom-built miniaturized CVD system capable of observing and recording 2D MoS2 crystal growth in real time. Image processing converts the real-time footage into digital data, and machine learning algorithms (ML) unveil the significant factors influencing growth. The machine learning model successfully predicts CVD growth parameters for synthesizing ultralarge monolayer MoS2 crystals. It also demonstrates the potential to reverse engineer CVD growth parameters by analyzing the as-grown 2D crystal morphology. This interdisciplinary approach can be integrated to enhance our understanding of controlled 2D crystal synthesis through CVD.

Chiral Soliton Lattice turns into 3D crystal

Chiral perturbation theory predicts the chiral anomaly to induce a so-called Chiral Soliton Lattice at sufficiently large magnetic fields and baryon chemical potentials. This state breaks translational invariance in the direction of the magnetic field and was shown to be unstable with respect to charged pion condensation. Improving on previous work by considering a realistic pion mass, we employ methods from type-II superconductivity and construct a three-dimensional pion (and baryon) crystal perturbatively, close to the instability curve of the Chiral Soliton Lattice. We find an analogue of the usual type-I/type-II transition in superconductivity: along the instability curve for magnetic fields eB > 0.12 GeV2 and chemical potentials μ < 910 MeV, this crystal can continuously supersede the Chiral Soliton Lattice. For smaller magnetic fields the instability curve must be preceded by a discontinuous transition.

Two-Dimensional Nonbenzenoid Heteroacene Crystals Synthesized via In-Situ Embedding of Ladder Bipyrazinylenes on Au(111).

Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π-electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two-dimensional (2D) crystals on surfaces is still a great challenge. By in-situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds. Using bond-resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o-diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms.

High frequency magnetometry with an ensemble of spin qubits in hexagonal boron nitride

Sensors based on spin qubits in 2D crystals offer the prospect of nanoscale proximities between sensor and source, which could provide access to otherwise inaccessible signals. For AC magnetometry, the sensitivity and frequency range are typically limited by the noise spectrum, which determines the qubit coherence time. We address this using phase modulated continuous concatenated dynamic decoupling, which extends the coherence time towards the T1 limit at room temperature and enables tuneable narrowband AC magnetometry. Using an ensemble of negatively charged boron vacancies in hexagonal boron nitride, we detect out-of-plane AC fields in the range of ~ 10 − 150 MHz, and in-plane fields within ± 150 MHz of the electron spin resonance. We measure an AC magnetic field sensitivity of sim 1,mu {{{rm{T}}}}/sqrt{{{{rm{Hz}}}}} at ~ 2.5 GHz, for a sensor volume of ~ 0.1 μm3. This work establishes the viability of spin defects in 2D materials for high frequency magnetometry, with wide-ranging applications across science and technology.

Formation of two-dimensional diamond-like colloidal crystals using layer-by-layer electrostatic self-assembly.

We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 μm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.

Giant auxetic behavior in remote-plasma synthesized few-layer tungsten semicarbide.

Auxetic crystals exhibiting highly positive lateral expansivity when stretched are an experimentally elusive class of two-dimensional (2D) materials with tremendous potential, for example in the direct transduction of electric signals and the compensation of thermal expansion at the nanoscale. 2D tungsten semi-carbide (W2C) was theoretically predicted to exhibit giant auxetic behavior, but has yet to be synthesized, as the corresponding full carbide (WC) is energetically favored under thermodynamic equilibrium synthesis processes such as furnace-based chemical vapor deposition. Here, we report on an ad hoc designed dual-zone remote plasma deposition system specially conceived to grow tungsten carbides out of thermodynamic equilibrium with well-tuned ratios of W and C precursors. We report on the specific conditions under which this system allowed for the synthesis of flakes of few-layer tungsten semicarbide (FL-W2C) which are 2D in nature due to retained periodicity at the mesoscopic level in a Stranski-Krastanov growth process. Under applied strain, FL-W2C 2D crystals exhibit the strongest auxetic behavior observed to date. This result suggests that the theoretically predicted high negative Poisson's ratio of single-layer W2C, also extends to thicker FL-W2C flakes that are retaining the periodicity of the 2D crystal at the mesoscopic level.

Encapsulation of crystalline and amorphous Sb2S3 within carbon and boron nitride nanotubes.

The recent rediscovery of 1D and quasi-1D (q-1D) van der Waals (vdW) crystals has laid foundation for the realization of emergent electronic, optical, and quantum-confined physical phenomena in both bulk and at the nanoscale. Of these, the highly anisotropic q-1D vdW crystal structure and the visible-light optical/optoelectronic properties of antimony trisulfide (Sb2S3) have led to its widespread consideration as a promising building block for photovoltaic and non-volatile phase change devices. However, while these applications will greatly benefit from well-defined and sub-nanometer-thick q-1D structures, little has been known about feasible synthetic routes that can access single covalent chains of Sb2S3. In this work, we explore how encapsulation in single or multi-walled carbon nanotubes (SWCNTs or MWCNTs) and visible-range transparent boron nitride nanotubes (BNNTs) influences the growth and phase of Sb2S3 nanostructures. We demonstrate that nanotubes with smaller diameters had a more pronounced effect in the crystallographic growth direction and orientation of Sb2S3 nanostructures, promoting the crystallization of the guest structures along the long-axis [010]-direction. As such, we were able to reliably access well-ordered few to single covalent chains of Sb2S3 when synthesized within defect-free SWCNTs with sub-2 nm inner diameters. Intriguingly, we found that the degree of crystalline order of Sb2S3 nanostructures was strongly influenced by the presence of defects and discontinuities along the Sb2S3-nanotube interface. We show that amorphous nanowire domains of Sb2S3 form around defect sites in larger, multi-walled nanotubes that manifest inner wall defects and discontinuities, suggesting a means to manipulate the crystallization dynamics of confined sub-10 nm-thick Sb2S3 nanostructures within nanotubes. Lastly, we show that ultranarrow amorphous Sb2S3 can impart functionality onto isolable BNNTs with photocurrent generation in the pA range which, alongside the dispersibility of the Sb2S3@BNNTs, could be leveraged to easily fabricate photoresistors only a few nm in width. Altogether, our results serve to solidify the understanding of how q-1D vdW pnictogen chalcogenides crystallize within confined synthetic platforms and are a step towards realizing functional materials from ensembles of encapsulated heterostructures.

Hofmeister effect-driven superlattice construction via hydrophilic/hydrophobic transition of poly(ethylene glycol) ligands

A Hofmeister effect-driven strategy for the directive construction of poly(ethylene glycol)-tethered nanoparticles into 2D superlattices, 3D single crystals, and multiply twinned superlattices through controlling the dehydration degree of ligands.

Fast thickness mapping of large-area exfoliated two-dimensional transition metal dichalcogenides by imaging spectroscopic ellipsometry

Two-dimensional transition metal dichalcogenides (2D TMDCs) have gained significant attention from the scientific community due to their exceptional properties, making them extremely attractive for optoelectronic and photonic applications. However, many exfoliation or synthesis techniques yield 2D crystals with limited crystalline quality and/or small lateral size. Here, we report a facile Au-assisted exfoliation method, yielding high-quality, large-area monolayers with lateral sizes of hundreds of micrometers. A self-assembled monolayer of (3-aminopropyl)triethoxysilane (APTES) is employed to improve the adhesion between the 2D material and the target substrate, dramatically improving the yield and reliability of the exfoliation process. The monolayer nature of the final sample is then assessed by means of Imaging Spectroscopic Ellipsometry (iSE), which enables a quick and reliable thickness mapping over millimeter-sized areas.

Determination and investigation of defect domains in multi-shape monolayer tungsten disulfide.

Single-layer tungsten disulfide (WS2) is among the most widely investigated two-dimensional materials. Synthesizing it over large areas would enable the exploitation of its appealing optical and electronic properties in industrial applications. However, defects of different nature, concentration and distribution profoundly affect the optical as well as the electronic properties of this crystal. Controlling the defect density distribution can be an effective way to tailor the local dielectric environment and therefore the electronic properties of the system. In this work we investigate the defects in single-layer WS2, grown in different shapes by liquid phase chemical vapor deposition, where the concentration of certain defect species can be controlled by the growth conditions. The properties of the material are surveyed by means of optical spectroscopy, photoelectron spectroscopy and Kelvin probe force microscopy. We determine the chemical nature of the defects and study their influence on the optical and electronic properties of WS2. This work contributes to the understanding of the microscopic nature of the intrinsic defects in WS2, helping the development of defect-based technologies which rely on the control and engineering of defects in dielectric 2D crystals.

Growth of two-dimensional covalent organic frameworks on substrates: insight from microsecond atomistic simulations.

While growing two-dimensional covalent organic frameworks (2D COFs) on substrates holds promise for producing functional monolayers, the presence of many defects in the resulting crystals often hinders their practical applications. Achieving structural order while suppressing defect formation necessitates a detailed atomic-level understanding. The key lies in understanding the polymerization process with high nano-scale accuracy, which presents significant challenges. Here, we perform microsecond atomistic molecular dynamics simulations to describe the deposition and polymerization of cyclohexa-m-phenylene on metal substrates, closely mimicking experimental conditions. Our improved approach highlights that 2D polymerization occurs through monomer addition and island coalescence, with a pre-bonding stage allowing monomers/oligomers to dynamically adjust their configurations to the expanding island structures. Our results elucidate the mechanisms underlying the formation of vacancy and dislocation defects during 2D polymerization as well as their healing processes. Overall, our findings underscore the significant roles that high surface mobility, effective monomer-substrate anchoring, high framework rigidity, moderate monomer coordination, and low bonding rate play in forming large, extended 2D crystals while suppressing vacancy and dislocation defects. We demonstrate how these factors can be tuned through substrate selection, deposition rate modulation, and temperature control, thereby offering valuable insight for strategically optimizing on-surface 2D polymerizations.

Imaging the 3D microstructural changes of ice cream during meltdown.

Ice cream is a multiphase frozen dessert that often melts during distribution and upon consumption. The meltdown phenomenon is one of the concerns in the quality preservation of ice cream for consumer convenience in the frozen food industry. In this context, X-ray tomography was used to visualise and quantify 3D ice crystal and air bubble evolution during the meltdown of ice cream. Two ice cream products, namely I and II, with varying air volume fractions, were evaluated for this study. The results indicated a small mean diameter of 66.43 ± 2.07µm at 0min and decreased to 45.74 ± 3.92µm during 10min of the meltdown of ice cream II. A large mean diameter of ice crystals of 75.02 ± 3.14µm was found in ice cream I, at 0min that decreased significantly (p < 0.05) to 54.30 ± 2.63µm during 10min of the meltdown. The air bubbles were also observed to decrease in mean diameter. The 3D datasets on the ice crystals and air bubbles described in this work provide more insight into the 3D microstructural evolution during the meltdown and are useful in controlling the sensory quality attributes of ice cream desserts.

Study on the microcrystal cellulose and the derived 2D graphene and relative carbon materials

Microcrystal cellulose (MCC) is a green and sustainable resource that widely exists in various lignocellulose species in percentage 10% to 30%. The fine powder of MCC is often discarded in industrial productions that use lignocellulose as feedstock. The crystal structure of two types of MCC (sugarcane pith and bamboo pith) and their derived carbon materials are studied, and the key findings are summarized as follows. (1) In the MCC refined from sugarcane pith, there are large amount of cellulose 2D crystal, which can be converted to valuable 2D graphene crystal. (2) In the MCC refined from bamboo pith there are large amount of cluster microcrystal cellulose, which can be converted to soft and elastic graphene microcrystal (GMC). (3) The 2D cellulose in MCC of sugarcane pith has large surface area and is easily to be degraded to sugars by acid–base hydrolysis reaction, which can be carbonized to Fullerenes-like carbon spheres. (4) The crystal structures of MCC derived carbon materials are strongly impacted by the crystal structures of MCC, and the carbonization reaction of MCC follows “in situ carbonization” and “nearby recombination” mechanism. In general, the results from this study may open a new way for value-added applications of microcrystal cellulose.

Atomic‐Scale Insights into the 2D Materials from Aberration‐Corrected Scanning Transmission Electron Microscopy: Progress and Future

2D crystals are attractive due to their unique atomic, electronic structures, and physiochemical properties, which strongly rely on the synthesis conditions. The atomic structure and presence of defects in the crystal lattice, such as vacancies, dopants, grain boundaries, and edge terminations, significantly influence the properties of 2D materials. Due to its high spatial resolution, aberration‐corrected scanning transmission electron microscopy (AC‐STEM) has become a powerful tool to provide atomic‐scale insights into the crystal structure, defects, heterointerfaces, ferroelectricity, and in situ observations of 2D materials. This review will cover the status of atomic‐scale studies on various 2D materials, including graphene, boron nitride, transition metal dichaogenides, MXenes, and phosphorene using AC‐STEM. The future perspective of AC‐STEM for new findings in 2D materials using machine learning is further discussed.

2D MOFs and Zeolites for Composite Membrane and Gas Separation Applications: A Brief Review.

Commercial membranes have predominantly been fabricated from polymers due to their economic viability and processability. This choice offers significant advantages in energy efficiency, cost-effectiveness, and operational simplicity compared to conventional separation techniques like distillation. However, polymeric membranes inherently exhibit a trade-off between their permeability and selectivity, which is summarized in the Robeson upper bound. To potentially surpass these limitations, mixed-matrix membranes (MMMs) can be an alternative solution, which can be constructed by combining polymers with inorganic additives such as metal-organic frameworks (MOFs) and zeolites. Incorporating high-aspect-ratio fillers like MOF nanosheets and zeolite nanosheets is of significant importance. This incorporation not only enhances the efficiency of separation processes but also reinforces the mechanical robustness of the membranes. We outline synthesis techniques for producing two-dimensional (2D) crystals (including nanocrystals with high aspect ratio) and provide examples of their integration into membranes to customize separation performances. Moreover, we propose a potential trajectory for research in the area of high-aspect-ratio materials-based MMMs, supported by a mathematical-model-based performance prediction.

Chiral organic molecular structures supported by planar surfaces.

We employ the molecular dynamics simulations to study the dynamics of acetanilide (ACN) molecules placed on a flat surface of planar multilayer hexagonal boron nitride. We demonstrate that the ACN molecules, known to be achiral in the three-dimensional space, become chiral after being placed on the substrate. Homochirality of the ACN molecules leads to stable secondary structures stabilized by hydrogen bonds between peptide groups of the molecules. By employing molecular dynamics simulations, we reveal that the structure of the resulting hydrogen-bond chains depends on the isomeric composition of the molecules. If all molecules are homochiral (i.e., with only one isomer being present), they form secondary structures (chains of hydrogen bonds in the shapes of arcs, circles, and spirals). If the molecules at the substrate form a racemic mixture, then no regular secondary structures appear, and only curvilinear chains of hydrogen bonds of random shapes emerge. A hydrogen-bond chain can form a zigzag array only if it has an alternation of isomers. Such chains can create two-dimensional (2D) regular lattices or 2D crystals. The melting scenarios of such 2D crystals depend on density of its coverage of the substrate. At 25% coverage, melting occurs continuously in the temperature interval 295-365K. For a complete coverage, melting occurs at 415-470 K due to a shift of 11% of all molecules into the second layer of the substrate.

Hydrogen Transport Between Layers of Transition Metal‐Dichalcogenides

AbstractHydrogen is a crucial source of green energy and is extensively studied for its potential usage in fuel cells. The advent of 2D crystals (2DCs) has taken hydrogen research to new heights, enabling it to tunnel through layers of 2DCs or be transported within voids between the layers, as demonstrated in recent experiments by Geim's group. In this study, it investigates how the composition and stacking of transition‐metal dichalcogenide (TMDC) layers influence the transport and self‐diffusion coefficients (D) of hydrogen atoms using well‐tempered metadynamics (WTMetaD) simulations. The findings show that modifying either the transition metal or the chalcogen atoms significantly affects the free energy barriers (ΔF) and, consequently, the self‐diffusion of hydrogen atoms between the 2DC layers. In the polytype (2H stacking), MoSe2 exhibits the lowest ΔF, while WS2 has the highest, resulting in the largest D for the former system. Additionally, hydrogen atoms inside the (or 3R) polytype encounter more than twice lower energy barriers and, thus, much higher diffusivity compared to those within the most stable stacking. These findings are particularly significant when investigating twisted layers or homo‐ or heterostructures, as different stacking areas may dominate over others, potentially leading to directional transport and interesting materials for ion or atom sieving.

Polytypic Two-Dimensional FeAs with High Anisotropy.

In the realm of two-dimensional (2D) crystal growth, the chemical composition often determines the thermodynamically favored crystallographic structures. This relationship poses a challenge in synthesizing novel 2D crystals without altering their chemical elements, resulting in the rarity of achieving specific crystallographic symmetries or lattice parameters. We present 2D polymorphic FeAs crystals that completely differ from bulk orthorhombic FeAs (Pnma), differing in the stacking sequence, i.e., polytypes. Preparing polytypic FeAs outlines a strategy for independently controlling each symmetry operator, which includes the mirror plane for 2Q-FeAs (I4/mmm) and the glide plane for 1Q-FeAs (P4/nmm). As such, compared to bulk FeAs, polytypic 2D FeAs shows highly anisotropic properties such as electrical conductivity, Young's modulus, and friction coefficient. This work represents a concept of expanding 2D crystal libraries with a given chemical composition but various crystal symmetries.

Lateral epitaxial growth of two-dimensional organic heterostructures.

Two-dimensional organic lateral heterostructures (2D OLHs) are attractive for the fabrication of functional materials. However, it is difficult to control the nucleation, growth and orientation of two distinct components. Here we report the combination of two methods-liquid-phase growth and vapour-phase growth-to synthesize 2D OLHs from perylene and a perylenecarboxaldehyde derivative, with a lateral size of ~20 μm and a tunable thickness ranging from 20 to 400 nm. The screw dislocation growth behaviour of the 2D crystals shows the spiral arrangement of atoms within the crystal lattice, which avoids volume expansion and contraction of OLH, thereby minimizing lateral connection defects. Selective control of the nucleation and sequential growth of 2D crystals leads to structural inversion of the 2D OLHs by the vapour-phase growth method. The resulting OLHs show good light-transport capabilities and tunable spatial exciton conversion, useful for photonic applications. This synthetic strategy can be extended to other families of organic polycyclic aromatic hydrocarbons, as demonstrated with other pyrene and perylene derivatives.