Crystalline Monolayer Research Articles

2D constraint modifies packing behaviour: a halobenzene monolayer with X3 halogen-bonding motif

ABSTRACT Using a combination of X-ray diffraction and simulation techniques, we are able to identify a crystalline monolayer of 1,3,5-triiodotrifluorobenzene formed on graphite. The monolayer is found to exhibit an incommensurate hexagonal unit cell with a lattice parameter of 9.28(7) Å, exhibiting a trigonal arrangement of iodine atoms not found in the bulk structure. DFT simulations have been performed exhibiting close agreement with the experimental structure. Importantly these simulations can be used to compare the strength of the intermolecular interactions both with and without Van der Waals corrections. Thus it is possible to estimate that halogen bonding consists of approximately half the total interaction energy. This demonstrates that despite the presence of strong directional non-covalent bonding, dispersion interactions account for a very significant proportion of the total energy.

Is Ice Nucleation by Organic Crystals Nonclassical? An Assessment of the Monolayer Hypothesis of Ice Nucleation.

Potent ice nucleating organic crystals display an increase in nucleation efficiency with pressure and memory effect after pressurization that set them apart from inorganic nucleants. These characteristics were proposed to arise from an ordered water monolayer at the organic-water interface. It was interpreted that ordering of the monolayer is the limiting step for ice nucleation on organic crystals, rendering their mechanism of nucleation nonclassical. Despite the importance of organics in atmospheric ice nucleation, that explanation has never been investigated. Here we elucidate the structure of interfacial water and its role in ice nucleation at ambient pressure on phloroglucinol dihydrate, the paradigmatic example of outstanding ice nucleating organic crystal, using molecular simulations. The simulations confirm the existence of an interfacial monolayer that orders on cooling and becomes fully ordered upon ice formation. The monolayer does not resemble any ice face but seamlessly connects the distinct hydrogen-bonding orders of ice and the organic surface. Although large ordered patches develop in the monolayer before ice nucleates, we find that the critical step is the formation of the ice crystallite, indicating that the mechanism is classical. We predict that the fully ordered, crystalline monolayer nucleates ice above -2 °C and could be responsible for the exceptional ice nucleation by the organic crystal at high pressures. The lifetime of the fully ordered monolayer around 0 °C, however, is too short to account for the memory effect reported in the experiments. The latter could arise from an increase in the melting temperature of ice confined by strongly ice-binding surfaces.

Promoting a Weak Coupling of Monolayer MoSe2 Grown on (100)-Faceted Au Foil.

As a two-dimensional semiconductor with many physical properties, including, notably, layer-controlled electronic bandgap and coupled spin-valley degree of freedom, monolayer MoSe2 is a strong candidate material for next-generation opto- and valley-electronic devices. However, due to substrate effects such as lattice mismatch and dielectric screening, preserving the monolayer's intrinsic properties remains challenging. This issue is generally significant for metallic substrates whose active surfaces are commonly utilized to achieve direct chemical or physical vapor growth of the monolayer films. Here, we demonstrate high-temperature-annealed Au foil with well-defined (100) facets as a weakly interacting substrate for atmospheric pressure chemical vapor deposition of highly crystalline monolayer MoSe2. Low-temperature scanning tunneling microscopy/spectroscopy measurements reveal a honeycomb structure of MoSe2 with a quasi-particle bandgap of 1.96 eV, a value comparable with other weakly interacting systems such as MoSe2/graphite. Density functional theory calculations indicate that the Au(100) surface exhibits the preferred energetics to electronically decouple from MoSe2, compared with the (110) and (111) crystal planes. This weak coupling is critical for the easy transfer of monolayers to another host substrate. Our study demonstrates a practical means to produce high-quality monolayers of transition-metal dichalcogenides, viable for both fundamental and application studies.

Highly crystalline Mo1-xRexS2 monolayers by NaCl-assisted and space-confined chemical vapor deposition

Alloy engineering is of great importance in expanding the two-dimensional (2D) material family and modulating the bandgap of atomically thin 2D transition metal dichalcogenides (TMDs). Here, we report the synthesis of large area and high quality 2H Mo1-xRexS2 (x<=0.02) monolayer crystals by NaCl-assisted and space-confined chemical vapor deposition strategy. The combined effects of both common salt and confined space help promote the growth of Mo1-xRexS2 alloy monolayer crystals. The as-grown Mo1-xRexS2 alloy monolayers are uniformly distributed on the whole growth substrates with a domain size of up to 90 μm. Optical images, X-ray spectroscopy, Raman and photoluminescence spectroscopy measurements and corresponding mapping figures reflect the high quality and uniformity of the monolayers. The Mo1-xRexS2 alloy based phototransistor device exhibit good photoresponse to visible light with a response time of less than 0.2 s. Such alloy engineering of atomically thin 2D TMDs is useful for their future applications in optoelectronics.

Structured liquids with interfacial robust assemblies of a nonionic crystalline surfactant

HypothesisThe structuring of liquids, that is, the kinetic trapping of nonequilibrium shapes of liquid–liquid interfaces, shows great promise for various applications, especially all-liquid devices. The strategies reported thus far to stabilize such unstable states include interfacial jamming of large colloidal particles and interfacial coassembly of elaborate molecules and/or nanoparticles. However, the structuring of liquids using a simple molecular surfactant has not been sufficiently demonstrated. We hypothesized that a surfactant with strong intermolecular interactions would form interfacial assemblies that behave substantially as solid particles for the structuring of liquids. Experimentsn-Octyl cello-oligosaccharide, a novel nonionic surfactant developed recently was explored as a candidate because of the ability of cello-oligosaccharides to form robust crystalline assemblies. Interfacial assembly of the nonionic crystalline surfactant was investigated for various water–organic solvent interfaces via pendant drop tensiometry and emulsification. FindingsThe crystalline surfactant was found to self-assemble and form a crystalline monolayer at water–organic solvent interfaces, allowing arrested shape changes of the liquid–liquid interfaces. Irregular-shaped liquid droplets were successfully created under various solution conditions, such as various organic solvents for the oil phase and the water phase with high ionic strengths and harsh pH values.

Hexagonal metal oxide monolayers derived from the metal-gas interface.

Two-dimensional (2D) crystals are promising materials for developing future nano-enabled technologies1-6. The cleavage of weak, interlayer van der Waals bonds in layered bulk crystals enables the production of high-quality 2D, atomically thin monolayers7-10. Nonetheless, as earth-abundant compounds, metal oxides are rarely accessible as pure and fully stoichiometric monolayers owing to their ion-stabilized 'lamellar' bulk structure11-14. Here, we report the discovery of a layered planar hexagonal phase of oxides from elements across the transition metals, post-transition metals, lanthanides and metalloids, derived from strictly controlled oxidation at the metal-gas interface. The highly crystalline monolayers, without the support of ionic dopants or vacancies, can easily be mechanically exfoliated by stamping them onto substrates. Monolayer and few-layered hexagonal TiO2 are characterized as examples, showing p-type semiconducting properties with hole mobilities of up to 950 cm2 V-1 s-1 at room temperature. The strategy can be readily extended to a variety of elements, possibly expanding the exploration of metal oxides in the 2D quantum regime.

Organic crystalline monolayers for ideal behaviours in organic field-effect transistors

In this work, ideal OFETs have been obtained by a facile and effective method, i.e. phase-separation between polymer and small molecules, and the generated monolayer crystals are beneficial for reducing contact resistance and interfacial trap density.

Reaping the catalytic benefits of both surface (NiFe2O4) and underneath (Ni3Fe) layers for the oxygen evolution reaction

Facile growth of a crystalline monolayer of NiFe2O4 encompassing Ni3Fe embedded within a polyaniline matrix for the oxygen evolution reaction.

Mechanism of surface freezing of alkanes.

Using molecular dynamics simulation of octane (C8) and nonadecane (C19), we probe the mechanism of n-alkane surface freezing, the appearance of a crystalline monolayer above the liquid at a temperature Tsf above the bulk freezing point Tf. Formation of a crystalline monolayer occurs robustly in these systems. When Tf > Tsf, the surface frozen phase is metastable with respect to the solid but persists for long periods for study in simulations. Surface freezing of both C8 and C19 is driven by significant energy-lowering when alkane chains become ordered along the surface normal, and we elucidate the origins of this phenomenon. The degree of configurational disorder in the surface frozen layer relative to the solid is much larger for C8 compared to C19. From the Gibbsian viewpoint, we extract the excess energy and entropy of the liquid and surface frozen phases. We also consider the surface frozen layer as an intervening third phase, the viewpoint taken in previous theoretical analyses. Here, we find significantly increased entropy of the surface frozen phase of C8 associated with configurational disorder, while the energy and entropy of the surface frozen phase of C19 are marginally different from the bulk solid. Finally, by combining our previously determined solid-vapor surface free energies of C8 and C19 with liquid-vapor surface tensions from this work, we eliminate wetting as a possible mechanism for C8 surface freezing, but it remains a possibility for C19. We analyze the molecular structure of the liquid, surface frozen, and solid surfaces and discuss its relevance to thermodynamic properties.

Partitioning the interlayer space of covalent organic frameworks by embedding pseudorotaxanes in their backbones.

Mono- or few-layer sheets of covalent organic frameworks (COFs) represent an attractive platform of two-dimensional materials that hold promise for tailor-made functionality and pores, through judicious design of the COF building blocks. But although a wide variety of layered COFs have been synthesized, cleaving their interlayer stacking to obtain COF sheets of uniform thickness has remained challenging. Here, we have partitioned the interlayer space in COFs by incorporating pseudorotaxane units into their backbones. Macrocyclic hosts based on crown ethers were embedded into either a ditopic or a tetratopic acylhydrazide building block. Reaction with a tritopic aldehyde linker led to the formation of acylhydrazone-based layered COFs in which one basal plane is composed of either one layer, in the case of the ditopic macrocyclic component, or two adjacent layers covalently held together by its tetratopic counterpart. When a viologen threading unit is introduced, the formation of a host-guest complex facilitates the self-exfoliation of the COFs into crystalline monolayers or bilayers, respectively.

Printable two-dimensional superconducting monolayers.

Two-dimensional superconductor (2DSC) monolayers with non-centrosymmetry exhibit unconventional Ising pair superconductivity and an enhanced upper critical field beyond the Pauli paramagnetic limit, driving intense research interest. However, they are often susceptible to structural disorder and environmental oxidation, which destroy electronic coherence and provide technical challenges in the creation of artificial van der Waals heterostructures (vdWHs) for devices. Herein, we report a general and scalable synthesis of highly crystalline 2DSC monolayers via a mild electrochemical exfoliation method using flexible organic ammonium cations solvated with neutral solvent molecules as co-intercalants. Using NbSe2 as a model system, we achieved a high yield (>75%) of large-sized single-crystal monolayers up to 300 µm. The as-fabricated, twisted NbSe2 vdWHs demonstrate high stability, good interfacial properties and a critical current that is modulated by magnetic field when one flux quantum fits to an integer number of moiré cells. Additionally, formulated 2DSC inks can be exploited to fabricate wafer-scale 2D superconducting wire arrays and three-dimensional superconducting composites with desirable morphologies.

NaCl-assisted substrate dependent 2D planar nucleated growth of MoS2

Synthesis of large-scale, uniform, easily transferable, and highly crystalline monolayer (1L) molybdenum disulfide (MoS2) on different substrates is a challenge and could decide its suitability for opto-electronic device applications. Herein, we report a facile NaCl-assisted Chemical Vapor Deposition (CVD) synthesis of high-quality MoS2 on amorphous, crystalline and layered substrates. Optical microscopy and Raman spectroscopy show that sapphire and SiO2/Si are suitable substrates for large 1L-MoS2 flakes growth, while mica is excellent for large-area continuous films. Comparatively lesser full-width-at-half-maximum (FWHM) of predominant A exciton peak in photoluminescence spectra of 1L-MoS2 on sapphire suggests its high crystalline quality. However, 1L-MoS2 on other substrates, especially on quartz and bare Si show poor crystalline quality. The study depicts that the NaCl assists in the formation of seeding promoter such as water-soluble layer of Na2S and/or Na2SO4 on the substrate that helps in 2D planar nucleation of MoS2. The formation of such intermediate seeding layers also helps in layer transfer owing to its easy water solubility. The study could be utilized for large-scale synthesis of 1L-MoS2 on different substrates for high-performance optoelectronic devices.

Atomic-Scale Studies of Overlapping Grain Boundaries between Parallel and Quasi-Parallel Grains in Low-Symmetry Monolayer ReS2

Summary Grain boundaries (GBs) are significant microstructures that dominate properties of polycrystalline two-dimensional (2D) materials. Low-symmetry rhenium disulfide monolayers provide an ideal platform to investigate diverse configurations of GBs and their orientation-dependent characteristics. Here, we utilize the preferential deposition of platinum-based nanoparticles on grain edges to rapidly locate nanoscale-wide overlapping GBs during microscopic-scale observation. Atomic-resolution investigations by aberration-corrected annular dark-field scanning transmission electron microscopy reveal diverse overlapping GBs constructed by parallel grains with transversal displacement. They prefer to align along several primary lattice directions with different interlayer atomic registries. Calculations show that the electronic band structures of overlapping GBs are strongly direction dependent, suggesting their potential in tunable electronic and photonic devices. Incommensurate overlapping GBs formed by quasi-parallel grains with ultrasmall twist angles are also observed. These results unveil the rich polymorphism of GBs and new opportunities to tailor properties of anisotropic 2D materials via GB engineering.

Unidirectional growth of graphene nano-islands from carbon cluster seeds on Ge(1 1 0)

The anisotropic twofold symmetry of Ge(110) makes it a unique substrate for the growth of single-crystalline graphene. However, the underlying mechanism during the initial stage of growth of graphene on Ge(110) surface is not well understood. Here, we use in-situ cryogenic scanning tunneling microscopy (STM) and spectroscopy (STS), to study the initial growth properties of graphene synthesized on Ge(110) surface with ethylene precursor gases. The STM results reveal that the unidirectional growth of the graphene nanoribbons (GNRs) initiates from carbon cluster seeds on terraces during the early stage of the growth. The orientations of the GNRs show the same directions which are nearly parallel to the 1¯10direction of the Ge(110) surface. This orientation is the same as that of the wafer-scale graphene grown on Ge(110). Subsequent growth, transformed the GNRs to graphene nanoislands (GNIs), which eventually coalesced to form single crystalline monolayer graphene. STS measurements demonstrated that the GNRs have small bandgaps induced by the confinement effect of graphene. This study provides an in-depth understanding of the growth mechanism of graphene on Ge(110) surface in various synthesis conditions.

Liquid metal-based synthesis of high performance monolayer SnS piezoelectric nanogenerators

The predicted strong piezoelectricity for monolayers of group IV monochalcogenides, together with their inherent flexibility, makes them likely candidates for developing flexible nanogenerators. Within this group, SnS is a potential choice for such nanogenerators due to its favourable semiconducting properties. To date, access to large-area and highly crystalline monolayer SnS has been challenging due to the presence of strong inter-layer interactions by the lone-pair electrons of S. Here we report single crystal across-the-plane and large-area monolayer SnS synthesis using a liquid metal-based technique. The characterisations confirm the formation of atomically thin SnS with a remarkable carrier mobility of ~35 cm2 V−1 s−1 and piezoelectric coefficient of ~26 pm V−1. Piezoelectric nanogenerators fabricated using the SnS monolayers demonstrate a peak output voltage of ~150 mV at 0.7% strain. The stable and flexible monolayer SnS can be implemented into a variety of systems for efficient energy harvesting.

Ultrafast nucleation and growth of high-quality monolayer MoSe2 crystals via vapor-liquid-solid mechanism

The controlled production of two-dimensional atomically thin transition metal dichalcogenides (TMDs) is fundamentally important for their device applications. However, the synthesis of large-area and high-quality TMD monolayers remains a challenge due to the lack of sufficient understanding of growth mechanisms, especially for the chemical vapor deposition (CVD). Here we report molten-salt assisted CVD growth of highly crystalline MoSe2 monolayers via a novel vapor-liquid-solid (VLS) mechanism. Our results show that the growth rate of the VLS-grown monolayer MoSe2 is about 40 times faster than that of MoSe2 grown via the vapor-solid (VS) mechanism, which makes the fabrication of 100 μm domains for ∼2 min and a uniform monolayer film within 5 min. The ultrafast growth of monolayer MoSe2 crystals benefits from the synergic effect of one-dimensional VLS growth and two-dimensional VS edge expansion. Moreover, these MoSe2 monolayers exhibit high crystal quality and enhanced photoluminescence due to efficient Se-vacancy repairing by the doping of halogen atoms. These findings provide a new understanding of MoSe2 growth and open up an opportunity for the rapid synthesis of high-quality TMD monolayers and heterostructures.

Preparation of a Si(111) Atomically Flat Substrate via Wet Etching and Evaluation as an AFM Substrate for Observations of Isolated Chains, Crystals, and Crystallization of Isotactic Poly(methyl methacrylate) at the Molecular Level.

To observe a polymer chain deposited on a substrate by atomic force microscopy (AFM) at the molecular level, the substrate should be atomically flat and stable under laboratory conditions and adsorb polymer chains firmly. Therefore, substrates used under laboratory conditions are practically limited to mica, highly ordered pyrolytic graphite, and atomically stepped sapphire, and polymers observed by AFM at the molecular level are also limited. A silicon wafer is frequently used as a substrate for AFM observation for somewhat macroscopic observations, but the surface of the silicon wafer is too rough to observe polymer chains deposited on it at the molecular level. In this study, we prepared an atomically stepped Si(111) substrate via wet etching in NH4F and evaluated it as an AFM substrate. The Si(111) substrate was stable as an AFM substrate, and isolated poly(methyl methacrylate) (it-PMMA) chains and a crystalline monolayer deposited on the substrate were observed by AFM at the molecular level. An it-PMMA amorphous monolayer deposited on mica crystallized under high humidity, but that on the Si(111) substrate did not because of the difference in the surface nature and the crystal structure of the substrates. The Si(111) substrate was hydrophobic, and the it-PMMA monolayers could be deposited as a multilayer, which could not be formed on hydrophilic mica. The crystallization behavior of an it-PMMA amorphous multilayer and an amorphous/crystalline mixed multilayer on the Si(111) substrate was also evaluated.

Polyhedral Water Droplets: Shape Transitions and Mechanism.

While classical liquid droplets are rounded, transitions have recently been discovered which render polyhedral water-suspended droplets of several oils. Yet, the mechanism of these transitions and the role of the droplets' interfacial curvature in inducing these transitions remain controversial. In particular, one of the two mechanisms suggested mandates a convex interface, in a view from the oil side. Here we show that oil-suspended water droplets can spontaneously assume polyhedral shapes, in spite of their concave interface. These results strongly support the alternative mechanism, where the faceting in both oil and water droplets is driven by the elasticity of a crystalline monolayer, known to self-assemble at the oil-water interface, independent of its curvature. The faceting transitions in the water droplets allow the fundamental elastic properties of two-dimensional matter to be probed, enable new strategies in faceted nanoparticle and nanoshell synthesis, and provide insight into the molecular mechanisms of morphogenesis.

Remarkable surface-enhanced Raman scattering of highly crystalline monolayer Ti3C2 nanosheets

As a powerful non-destructive and label-free detection technology, surface-enhanced Raman scattering (SERS) has been widely used in environmental-pollutant detection, biological-tissue sensing, molecular fingerprint analysis and so on. Different from the traditional SERS substrates represented by noble metals and semiconductors, herein, we report a new highly sensitive SERS substrate material with high stability, biocompatibility, and low cost, namely nucleusfree two-dimensional electron gas (2DEG) Ti3C2 monolayer nanosheets. The highly crystalline monolayer Ti3C2 nanosheets with clean surface are synthesized by an improved chemical exfoliation and microwave heating method. The unique structure of nucleus-free-2DEG in Ti3C2 monolayer provides an ideal transport channel without nuclear scattering, which makes the highly crystalline monolayer Ti3C2 nanosheets achieve a Raman enhanced factor of 3.82×108 and a 10−11 level detection limit for typical environmental pollutants such as azo dyes, trichlorophenol, and bisphenol A. Single-molecule imaging is also realized on the surface of the Ti3C2 monolayers, which may be the first time that approximate single-molecule imaging has been achieved on a non-noblemetal SERS substrates. Preliminary toxicological experiments show that the cytotoxicity of this material is very low. Considering the facile synthesis, high biocompatibility, low cost and high chemical stability of carbide nanosheets, these Ti3C2 monolayer nanosheets show significant promise for the design and fabrication of flexible SERS substrates for the sensing of trace substances with ultrahigh sensitivity.

Floating layers and thin films of mesogenic mix-substituted phthalocyanine holmium complex

The supramolecular organization of the A3B-type phthalocyanine holmium complex (A3B–Ho) was investigated in floating layers at the air–water interface and in Langmuir-Schaefer thin films at the air–solid interface. The floating layers formed under different experimental conditions on the water subphase using the Langmuir technique. They were studied by Brewster angle microscopy, grazing incidence X-ray diffraction and X-ray reflectometry. It was established that molecules of A3B–Ho form stable ordered floating monolayer on the water surface. Experimental conditions required for this monolayer formation were determined as following: the initial degree of coating of the water surface was 18%, the compression rate of barriers was 6 cm2/min and the surface pressure was 0.4 mN/m. Under these conditions a stable crystalline monolayer structure was obtained with an area per one molecule 3.9 nm2. It has a two-dimensional face-on packing with the intralayer period of 2.06 nm. The Langmuir-Schaefer thin film was obtained on the basis of the above mentioned monomolecular floating layer. The film possesses a single two-dimensional structure with the packing of the molecules parralel to the substrate surface that was revealed by electron diffraction. The lattice parameters of the monomolecular film were a = 1.65 nm, b = 1.92 nm, γ1 = 75. It was shown that the film preserves the structure of the floating monolayer.