Crystalline Monolayer Research Articles

Reduction of a two-dimensional crystalline MoO3 monolayer

The atomic structure of MoOx films formed upon a gradual thermal reduction of an ordered MoO3 monolayer on the Pd(100) substrate was explored via surface science characterization techniques and density functional theory (DFT) calculations. Two main reduction stages were identified. First, the initial oxygen excess was gradually eliminated by altering the domain boundary length, orientation, and atomic structure. The films nevertheless remained O-rich, with numerous terminal oxygen atoms (formation of MoO groups), and an elevated work function. Second, multiple ordered O-lean phases were formed, characterized by either very few or no terminal oxygen atoms, and a much smaller surface work function. According to calculations, the positive charging of the Pd substrate stabilizes the oxygen excess during the first stage, but during the second reduction stage, the substrate becomes negatively charged, stabilizing enhanced cation oxidation states. On their basis, the mechanisms underlying the oxygen release from the initial c(2 × 2) domains were disclosed. The experiments showed that the film reduction is perfectly reversible, which highlights the very promising properties of the MoO3/Pd system for heterogeneous catalysis.

Programmable Crowding and Tunable Phases in a Binary Mixture of Colloidal Particles under Light-Driven Thermal Convection.

We employ photothermally driven self-assembly of colloidal particles to design microscopic structures with programmable size and tunable order. The experimental system is based on a binary mixture of "plasmonic heater" gold nanoparticles and "assembly building block" microparticles. Photothermal heating of the gold nanoparticles under visible light causes a natural convection flow that efficiently assembles the microscale building block particles (diameter 1-10 μm) into a monolayer. We identify the onset of active Brownian motion of colloidal particles under this convective flow by varying the conditions of light intensity, gold nanoparticle concentration, and sample height. We realize a crowded assembly of microparticles around the center of illumination and show that the size of the particle crowd can be programmed using patterned light illumination. In a binary mixture of gold nanoparticles and polystyrene microparticles, we demonstrate the formation of rapid and large-scale crystalline monolayers, covering an area of 0.88 mm2 within 10 min. We find that the structural order of the assembly can be tuned by varying the surface charge of the nanoparticles and the size of the microparticles, giving rise to the formation of different phases-colloidal crystals, crowds, and gels. Using Monte Carlo simulations, we explain how the phases emerge from the interplay between hydrodynamic and electrostatic interactions, as well as the assembly kinetics. Our study demonstrates the promise of self-assembly with programmable shapes and structural order under nonequilibrium conditions using an accessible setup comprising only binary mixtures and LED light.

Non-Classical Euler Buckling and Brazier Instability in Cylindrical Liquid Droplets.

Crystalline monolayers prevalent in nature and technology possess elusive elastic properties with important implications in fundamental physics, biology, and nanotechnology. Leveraging the recently discovered shape transitions of oil-in-water emulsion droplets, upon which these droplets adopt cylindrical shapes and elongate, we investigate the elastic characteristics of the crystalline monolayers covering their interfaces. To unravel the conditions governing Euler buckling and Brazier kink formation in these cylindrical tubular interfacial crystals, we strain the elongating cylindrical droplets within confining microfluidic wells. Our experiments unveil a nonclassical relation between the Young's modulus and the bending modulus of these crystals. Intriguingly, this relation varies with the radius of the cylindrical crystal, presenting a nonclassical mechanism for tuning of elasticity in nanotechnology applications.

Oleogelation: Triacontane crystals and hydrocarbon chain twisting. Theory and Monte Carlo simulations

AbstractThe molecular structure of a crystalline monolayer of hydrocarbon chains was modeled and studied via computer simulation using the Metropolis Monte Carlo algorithm at a temperature T = 300 K. The only interactions in this system occur through Lennard‐Jones dispersion forces and short‐range atom‐atom repulsion. The intent was to establish whether the chains were either rigidly extended or twisted via the thermal formation of gauche bonds and apply the results to understand observations made on two possible oleogelators: triacontane and stearic acid. Specifically, we aimed to understand if their observed crystalline monolayer thicknesses are due to gauche‐bond‐shortened hydrocarbon chains oriented perpendicular to the monolayer surface, or to fully extended rigid chains oriented at a tilt angle with respect to the surface. The results showed that crystals of hydrocarbon chains did not include significant gauche bonds, so that all molecules were rigidly extended, thus explaining the experimental data previously reported. Accordingly, TC and SA dimer molecules are packed in crystalline multilayers with tilt angles in relation to the methyl group plane.

On-water surface synthesis of electronically coupled 2D polyimide-MoS2 van der Waals heterostructure

The water surface provides a highly effective platform for the synthesis of two-dimensional polymers (2DP). In this study, we present an efficient on-water surface synthesis of crystalline monolayer 2D polyimide (2DPI) through the imidization reaction between tetra (4-aminophenyl) porphyrin (M1) and perylenetracarboxylic dianhydride (M2), resulting in excellent stability and coverage over a large area (tens of cm2). We further fabricate innovative organic-inorganic hybrid van der Waals heterostructures (vdWHs) by combining with exfoliated few-layer molybdenum sulfide (MoS2). High-resolution transmission electron microscopy (HRTEM) reveals face-to-face stacking between MoS2 and 2DPI within the vdWH. This stacking configuration facilitates remarkable charge transfer and noticeable n-type doping effects from monolayer 2DPI to MoS2, as corroborated by Raman spectroscopy, photoluminescence measurements, and field-effect transistor (FET) characterizations. Notably, the 2DPI-MoS2 vdWH exhibits an impressive electron mobility of 50 cm2/V·s, signifying a substantial improvement over pristine MoS2 (8 cm2/V·s). This study unveils the immense potential of integrating 2D polymers to enhance semiconductor device functionality through tailored vdWHs, thereby opening up exciting new avenues for exploring unique interfacial physical phenomena.

Scalable Fabrication of High-Performance Self-Powered a-MoSe2 Thin-Film-Based Photodetectors on a-SiO2/Si Substrates.

Owing to its high stability, suitable absorption band gap, and fast response time, MoSe2 has attracted the most attention in transition-metal dichalcogenides (TMDCs) for photodetector (PD) applications. In this study, based on centimeter-scale smooth amorphous MoSe2 (a-MoSe2) thin films with thicknesses varying from 6.5 to 62.5 nm on a-SiO2/Si substrates prepared by polymer-assisted deposition, metal-semiconductor-metal-structured self-powered a-MoSe2 PDs are designed and fabricated. Our data show that the PD based on 9.5 nm thick a-MoSe2 thin film exhibits the highest values of photocurrent (Iph, 4.60 μA), photo-to-dark current ratio (PDCR, 3067), photoresponsivity (Rλ, 0.94 mA/W), and detectivity (D*, 4.29 × 1010 Jones), as well as the lowest values of noise-equivalent power (NEP, 2.33 × 10-11 W/Hz1/2) and photoresponse rise/decay time (61/58 ms) under a 405 nm laser with 5 mW power at zero bias, which are better than or comparable with those of previously reported PDs based on crystalline MoSe2 monolayers or other atomically thin 2D materials under bias voltage. The high-performance mechanism can be explained in terms of the energy band theory and volume modulation photoconductive gain model in a-MoSe2 with a spontaneous built-in electric field. Our work provides a scalable low-cost way for the design and fabrication of high-performance self-powered TMDC PDs.

A Monolayer Carbon Nitride on Au(111) with a High Density of Single Co Sites.

Carbon nitrides that expose atomically dispersed single-atom metals in the form of M-N-C (M = metal) sites are attractive earth-abundant catalyst materials that have been demonstrated in electrocatalytic conversion reactions. The catalytic performance is determined by the abundance of N-doped sites and the type of metal coordination to N, but challenges remain to synthesize pristine carbon nitrides with a high concentration of the most active sites and prepare homogeneously doped materials that allow for in-depth characterization of the M-N-C sites and quantitative evaluation of their catalytic performance. Herein, we have synthesized and characterized a well-defined monolayer carbon nitride phase on a Au(111) surface that exposes an exceedingly high concentration of Co-N4 sites. The crystalline monolayer carbon nitride, whose formation is controlled by an on-surface reaction between Co atoms and melamine on Au(111), is characterized by a dense array of 4- and 6-fold N-terminated pockets, whereof only the 4-fold pocket is found to be holding Co atoms. Through detailed characterization using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory modeling, we determine the atomic structure and chemical state of the carbon nitride network. Furthermore, we show that the monolayer carbon nitride structure is stable and reactive toward the electrocatalytic oxygen reduction reaction in alkaline electrolyte, with a quantitative performance metric that significantly exceeds comparable M-N-C-based catalyst types. The work demonstrates that high-density active catalytic sites can be created using common precursor materials, and the formed networks themselves offer an excellent platform for onward studies addressing the characteristics of M-N-C sites.

Composition and sequence-controlled conductance of crystalline unimolecular monolayers.

Understanding how the charge travels through sequence-controlled molecules has been a formidable challenge because of simultaneous requirements in well-controlled synthesis and well-manipulated orientation. Here, we report electrically driven simultaneous synthesis and crystallization as a general strategy to study the conductance of composition and sequence-controlled unioligomer and unipolymer monolayers. The structural disorder of molecules and conductance variations on random positions can be extremely minimized, by uniform synthesis of monolayers unidirectionally sandwiched between electrodes, as an important prerequisite for the reproducible measurement on the micrometer scale. These monolayers show tunable current density and on/off ratios in four orders of magnitude with controlled multistate and massive negative differential resistance (NDR) effects. The conductance of monolayer mainly depends on the metal species in homo-metal monolayers, while the sequence becomes a matter in hetero-metal monolayers. Our work demonstrates a promising way to release an ultra-rich variety of electrical parameters and optimize the functions and performances of multilevel resistive devices.

"Magic Numbers" in Self-Faceting of Alcohol-Doped Emulsion Droplets.

Oil-in-water emulsion droplets spontaneously adopt, below some temperature Td , counterintuitive faceted and complex non-spherical shapes while remaining liquid. This transition is driven by a crystalline monolayer formed at the droplets' surface. Here, weshow that ppm-level doping of the droplet's bulk by long-chain alcohols allows tuning Td by >50 °C, implying formation of drastically different interfacial structures. Furthermore, "magic" alcohol chain lengths maximize Td . This weshow to arise from self-assembly of mixed alcohol:alkane interfacial structures of stacked alkane layers, co-crystallized with hydrogen-bonded alcohol dimers. These structures are accounted for theoretically and resolved by direct cryogenic transmission electron microscopy (cryoTEM), confirming the proposed structures. The discovered tunability of key properties of commonly-used emulsions by minute concentrations of specific bulk additives should benefit these emulsions' technologicalapplicability.

Transition of a 2D crystal to a non-equilibrium two-phase coexistence state

In this paper, we present experimental observation of the transition of a 2D dust crystal to a non-equilibrium solid–liquid phase coexistence state. The experiments have been carried out in an L-shaped dusty plasma experimental device in a DC glow discharge argon plasma environment. Initially, a monolayer crystalline structure is formed, which is later transformed to a two-phase coexistence state using the background neutral pressure as a control parameter. Self-excited horizontal oscillations are found in the center of the monolayer prior to the appearance of the coexistence state. It is observed that a molten center coexists with a solid periphery. Various structural, thermodynamic, and dynamical quantities are used to characterize the phase state. The surface tension at the solid–liquid circular interface is also determined. A detailed parametric study is made to delineate the existence region of such a state. It is found that melting caused at the core is due to the onset of a localized Schweigert instability in the presence of a few stray particles beneath the top layer in that region.

Micrometer-size crystalline monolayer MoS2 domains obtained by sulfurization of molybdenum oxide ultrathin films

In this work, the formation of micrometer-size crystalline monolayer (1L) MoS2 flakes with triangular shape and a central multilayer core is obtained by the sulfurization at 800 °C of pre-deposited ultrathin MoOx films (1.2–1.8 nm) on c-sapphire substrates. The thickness uniformity, crystalline quality, doping and strain distribution in the MoS2 flakes as a function of the initial MoOx thickness was evaluated by micro-Raman (μR) mapping. The excellent crystalline quality of the triangular 1L-MoS2 flakes was confirmed by micro-photoluminescence (μPL) maps, showing a very intense peak at ∼1.85 eV, that decreases in the central part, as expected for multilayers MoS2. A biaxial strain of ∼0.38–0.4% was deduced from the μPL data, in perfect agreement with μR results. Our results show how the sulfurization of pre-deposited MoOx films on c-sapphire allows, under proper conditions, to obtain 1L-MoS2 flakes with quality comparable to the one typically reported by the conventional chemical vapour deposition, with important implications for device applications.

Wafer‐scale single‐crystalline MoSe2 and WSe2 monolayers grown by molecular‐beam epitaxy at low‐temperature — the role of island‐substrate interaction and surface steps

AbstractUltrathin two‐dimensional transition‐metal dichalcogenides (TMDs) have been pursued extensively in recent years for interesting physics and application potentials. For the latter, it is essential to synthesize crystalline TMD monolayers at wafer‐scale. Here, we report growth of single‐crystalline MSe2 (M = Mo, W) monolayers at wafer‐scale by molecular‐beam epitaxy at low temperatures (200–400°C) on nominally flat Au(1 1 1) substrates. The epifilms have low intrinsic defect densities of low 1012 cm−2. The grown films have then been exfoliated and transferred onto SiO2/Si by a wet chemical process, on which some optical measurements are performed, revealing high spatial uniformity of the samples. We also establish that MSe2 grows on Au via the van der Waals epitaxy mechanism, where a continuous film extends across the whole surface, overhangs atomic‐layer steps on substrate. We identify that the growth of highly crystalline MSe2 is promoted by an enhanced interaction between Au substrate and MSe2 islands rather than by the guidance of surface steps on substrate. The latter only arrests MSe2 lateral growth if they are multilayer high.Key points MBE growth of wafer‐scale highly crystalline TMD monolayers at low‐temperature is achieved. Island‐substrate interaction is found to play a critical role in vdW epitaxy of single‐crystalline TMDs on on‐axis substates. The TMD monolayers are of high uniformity and low intrinsic defect density.

Large-Area Monolayer n-Type Molecular Semiconductors with Improved Thermal Stability and Charge Injection

We fabricated monolayer n-type two-dimensional crystalline semiconducting films with millimeter-sized areas and remarkable morphological uniformity using an antisolvent-confined spin-coating method. The antisolvent can cause a downstream Marangoni flow, which improves the film morphologies. The deposited crystalline monolayer films exhibit excellent thermal stabilities after annealing, which reveals the annealing-induced enhancement of crystallinity. The transistors based on the n-type monolayer crystalline films show linear output characteristics and superior electron mobilities. The improved charge injection between monolayer films and Au electrodes results from the energy level shift as the films decrease to the monolayer, which leads to a lower injection barrier. This work demonstrates a promising method for fabricating air-stable, low-cost, high-performance, and large-area organic electronics.

Two-dimensional crystal phases of graphene monoxide

The possible existence and properties of different polytypes of graphene monoxide (GmO)---two-dimensional crystalline monolayers composed of equal numbers of C and O atoms---are investigated using density functional calculations. Structural parameters, electronic, and mechanical properties of the different phases, including the previously reported $\ensuremath{\alpha}$ and $\ensuremath{\beta}$ phases, are determined and compared. It is suggested that multiple phases of GmO can coexist in the same composite, but developing a synthesis process for single-phase GmO may be experimentally challenging. The phases exhibit band structures ranging from insulating to metallic. From an analysis of the calculated elastic moduli, it is concluded that all the GmO structures are softer than graphene and are likely to change their lattice parameters if present in a composite with graphene.

High-harmonic generation from artificially stacked 2D crystals.

We report a coherent layer-by-layer build-up of high-order harmonic generation (HHG) in artificially stacked transition metal dichalcogenides (TMDC) crystals in their various stacking configurations. In the experiments, millimeter-sized single crystalline monolayers are synthesized using the gold foil-exfoliation method, followed by artificially stacking on a transparent substrate. High-order harmonics up to the 19th order are generated by the interaction with a mid-infrared (MIR) driving laser. We find that the generation is sensitive to both the number of layers and their relative orientation. For AAAA stacking configuration, both odd- and even-orders exhibit a quadratic increase in intensity as a function of the number of layers, which is a signature of constructive interference of high-harmonic emission from successive layers. Particularly, we observe some deviations from this scaling at photon energies above the bandgap, which is explained by self-absorption effects. For AB and ABAB stacking, even-order harmonics remain below the detection level, consistent with the presence of inversion symmetry. Our study confirms our capability of producing nonperturbative high-order harmonics from stacked layered materials subjected to intense MIR fields without damaging samples. Our results have implications for optimizing solid-state HHG sources at the nanoscale and developing high-harmonics as an ultrafast probe of artificially stacked layered materials. Because the HHG process is a strong-field driven process, it has the potential to probe high-momentum and energy states in the bandstructure combined with atomic-scale sensitivity in real space, making it an attractive probe of novel material structures such as the Moiré pattern.

Silicon chambers for enhanced incubation and imaging of microfluidic droplets.

Droplet microfluidics has become a powerful tool in life sciences, underlying digital assays, single-cell sequencing or directed evolution, and it is making foray in physical sciences as well. Imaging and incubation of droplets are crucial, yet they are encumbered by the poor optical, thermal and mechanical properties of PDMS, a material commonly used in microfluidics labs. Here we show that Si is an ideal material for droplet chambers. Si chambers pack droplets in a crystalline and immobile monolayer, are immune to evaporation or sagging, boost the number of collected photons, and tightly control the temperature field sensed by droplets. We use the mechanical and optical benefits of Si chambers to image ≈1 million of droplets from a multiplexed digital assay - with an acquisition rate similar to the best in-line methods. Lastly, we demonstrate their applicability with a demanding assay that maps the thermal dependence of Michaelis-Menten constants with an array of ≈150 000 droplets. The design of the Si chambers is streamlined to avoid complicated fabrication and improve reproducibility, which makes Si a complementary material to PDMS in the toolbox of droplet microfluidics.

Spatial Control of Substitutional Dopants in Hexagonal Monolayer WS2: The Effect of Edge Termination

The ability tocontrol the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS2 , it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS2 monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.

Liquid Phase Isolation of SnS Monolayers with Enhanced Optoelectronic Properties.

Recent advances in atomically thin two dimensional (2D) anisotropic group IVA -VI metal monochalcogenides (MMCs) and their fascinating intrinsic properties and potential applications are hampered due to an ongoing challenge of monolayer isolation. Among the most promising MMCs, tin (II) sulfide (SnS) is an earth-abundant layered material with tunable bandgap and anisotropic physical properties, which render it extraordinary for electronics and optoelectronics. To date, however, the successful isolation of atomically thin SnS single layers at large quantities has been challenging due to the presence of strong interlayer interactions, attributed to the lone-pair electrons of sulfur. Here, a novel liquid phase exfoliation approach is reported, which enables the overcome of such strong interlayer binding energy. Specifically, it demonstrates that the synergistic action of external thermal energy with the ultrasound energy-induced hydrodynamic force in solution gives rise to the systematic isolation of highly crystalline SnS monolayers (1L-SnS). It is shown that the exfoliated 1L-SnS crystals exhibit high carrier mobility and deep-UV spectral photodetection, featuring a fast carrier response time of 400ms. At the same time, monolayer-based SnS transistor devices fabricated from solution present a high on/off ratio, complemented with a responsivity of 6.7 ×10-3 AW-1 and remarkable stability upon prolonged operation in ambient conditions. This study opens a new avenue for large-scale isolation of highly crystalline SnS and other MMC manolayers for a wide range of applications, including extended area nanoelectronic devices, printed from solution.

Crystalline Unipolymer Monolayer with High Modulus and Conductivity.

The synthesis of crystalline polymer with a well-defined orientated state and a two-dimensional crystalline size beyond a micrometer will be essential to achieve the highest physical feature of polymer material but remain challenging. Herein, we show the synthesis of the crystalline unipolymer monolayer with an unusual ultrahigh modulus that is higher than the ITO substrate and high conductance by simultaneous electrosynthesis and manipulation. We find that the polymer monolayer has fully extended in the vertical and unidirectional orientation, which is proposed to approach their theoretically highest density, modulus, and conductivity among all aggregation formations of the current polymer. The modulus and current density can reach 40 and 1000 times higher than their amorphous counterpart. It is also found that these monolayers exhibit the bias- and length-dependent multiple charge states and asymmetrically negative differential resistance (NDR) effect, indicating that this unique molecular tailoring and ordering design is promising for multilevel resistive memory devices. Our work demonstrates the creation of a crystalline polymer monolayer for approaching the physical limit of polymer electronic materials and also provides an opportunity to challenge the synthetically iterative limit of an isolated ultra-long polymer.

Crystalline Unipolymer Monolayer with High Modulus and Conductivity

AbstractThe synthesis of crystalline polymer with a well‐defined orientated state and a two‐dimensional crystalline size beyond a micrometer will be essential to achieve the highest physical feature of polymer material but remain challenging. Herein, we show the synthesis of the crystalline unipolymer monolayer with an unusual ultrahigh modulus that is higher than the ITO substrate and high conductance by simultaneous electrosynthesis and manipulation. We find that the polymer monolayer has fully extended in the vertical and unidirectional orientation, which is proposed to approach their theoretically highest density, modulus, and conductivity among all aggregation formations of the current polymer. The modulus and current density can reach 40 and 1000 times higher than their amorphous counterpart. It is also found that these monolayers exhibit the bias‐ and length‐dependent multiple charge states and asymmetrically negative differential resistance (NDR) effect, indicating that this unique molecular tailoring and ordering design is promising for multilevel resistive memory devices. Our work demonstrates the creation of a crystalline polymer monolayer for approaching the physical limit of polymer electronic materials and also provides an opportunity to challenge the synthetically iterative limit of an isolated ultra‐long polymer.