Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are unit-cell thick materials with tunable physical properties according to their size, morphology, and chemical composition. Their transition of lab-scale research to industrial-scale applications requires process development for the wafer-scale growth and scalable device fabrication. Herein, we report on a new type of atmospheric pressure chemical vapor deposition (APCVD) process that utilizes colloidal nanoparticles as process-scalable precursors for the wafer-scale production of TMD monolayers. Facile uniform distribution of nanoparticle precursors on the entire substrate leads to the wafer-scale uniform synthesis of TMD monolayers with the controlled size and morphology. Composition-controlled TMD alloy monolayers with tunable bandgaps can be produced by simply mixing dual nanoparticle precursor solutions in the desired ratio. We also demonstrate the fabrication of ultrathin field-effect transistors and flexible electronics with uniformly controlled performance by using TMD monolayers.

Capacity enhancement of polylithiated functionalized boron nitride nanotubes: an efficient hydrogen storage medium.

By using first principles density functional theory simulations, we report detailed geometries, electronic structures and hydrogen (H2) storage properties of boron nitride nanotubes (BNNTs) doped with selective polylithiated molecules (CLi2). We find that unsaturated bonding of Li-1s states with BNNT significantly enhances the system stability and hinders the Li-Li clustering effect, which can be detrimental for reversible H2 storage. The H2 adsorption mechanism is explained on the basis of polarization caused by the cationic Li+ of CLi2 molecules bonded with BNNT. The incident H2 molecules are adsorbed with BNNT-nCLi2 through electrostatic and van der Waals interactions. We find that with a maximum of 5.0% of CLi2 coverage on BNNT, an H2 gravimetric density of up to 4.41 wt% can be achieved with adsorption energies in the range of -0.33 eV per H2, which is suitable for ambient condition H2 storage applications.

Competition between Hückel's Rule and Jahn-Teller Distortion in Small Carbon Rings: A Quantum Monte Carlo Study.

Structural properties and energetics of carbon rings are studied with the diffusion Monte Carlo (DMC) method. Our DMC-based geometry optimization reveals that both polyynic C4n and cumulenic C4n + 2 rings exhibit bond length alternations for n ≥ 3, which is understood to be due to Jahn-Teller distortions. The bond length alternation even in a cumulenic (4n + 2) carbon ring was experimentally observed in a recently synthesized C18 molecule. From a comparison of the DMC cohesive energies of C4n with those of C4n + 2, we present a comprehensive picture of the competition between Hückel's rule and Jahn-Teller distortion in small carbon rings; the former is more dominant than the latter for n < 5 where C4n + 2 rings are more stable than C4n, while C4n rings are as stable as C4n + 2 for n < 5 where dimerization effects due to Jahn-Teller distortion are more important.

Rational design and observation of the tight interface between graphene and ligand protected nanocrystals.

Heterostructures constructed of graphene and colloidal nanocrystals provide a unique way to exploit the coupled physical properties of the two functional building blocks. Studying the interface structure between the two constituent materials is important to understand the formation mechanism and the resulting physical and chemical properties. Along with ab initio calculations, we elucidate that the bending rigidity and the strong van der Waals interaction of graphene to the metal surface guide the formation of a tight and conformal interface. Using theoretical foundations, we construct colloidal nanocrystal-graphene heterostructures with controlled interfacial structures and directly investigate the cross-sectional structures of them at high resolution by using aberration-corrected transmission electron microscopy. The experimental method and observations we present here will link the empirical methods for the formation of nanocrystal-graphene heterostructures to the mechanistic understanding of their properties.

Calcium-decorated carbon nanostructures for the selective capture of carbon dioxide.

The development of advanced materials for CO2 capture is of great importance for mitigating climate change. In this paper, we outline our discovery that calcium-decorated carbon nanostructures, i.e., zigzag graphene nanoribbons (ZGNRs), carbyne, and graphyne, have great potential for selective CO2 capture, as demonstrated via first-principles calculations. Our findings show that Ca-decorated ZGNRs can bind up to three CO2 molecules at each Ca atom site with an adsorption energy of ∼-0.8 eV per CO2, making them suitable for reversible CO2 capture. They adsorb CO2 molecules preferentially, compared with other gas molecules such as H2, N2, and CH4. Moreover, based on equilibrium thermodynamical simulations, we confirm that Ca-decorated ZGNRs can capture CO2 selectively from a gas mixture with a capacity of ∼4.5 mmol g-1 under ambient conditions. Similar results have been found in other carbon nanomaterials, indicating the generality of carbon based nanostructures for selective CO2 capture under ambient conditions.

Potential-controlled current responses from staircase to blip in single Pt nanoparticle collisions on a Ni ultramicroelectrode.

Collisions of electrocatalytic platinum (Pt) single nanoparticles (NPs) with a less electrocatalytic nickel (Ni) ultramicroelectrode (UME) surface were detected by amplification of the current by electrocatalysis of NPs. Two typical types of current responses, a current staircase or blip (or spike), in single NP collision experiments were observed at a time with a new system consisting of Pt NP/Ni UME/hydrazine oxidation. The staircase current response was obtained when the collided NPs were attached to the electrode and continued to produce electrocatalytic current. On the other hand, the blip current response was believed to be obtained when the NP attached but was deactivated. The different current responses depend on the different electrocatalytic reaction mechanism, characteristics of the NP, or the electrode material. How the deactivation of the electrocatalytic process affects on the current response of NP collision was investigated using the Ni UME. The current response of a single Pt NP collision is controllable from staircase to blip by changing the applied potential. The current response of the Pt NP was observed as a staircase response with 0 V (vs Ag/AgCl) and as a blip response with 0.1 V (vs Ag/AgCl) applied to the Ni UME.

Heavy fermions vs doped Mott physics in heterogeneous Ta-dichalcogenide bilayers.

Controlling and understanding electron correlations in quantum matter is one of the most challenging tasks in materials engineering. In the past years a plethora of new puzzling correlated states have been found by carefully stacking and twisting two-dimensional van der Waals materials of different kind. Unique to these stacked structures is the emergence of correlated phases not foreseeable from the single layers alone. In Ta-dichalcogenide heterostructures made of a good metallic "1H"- and a Mott insulating "1T"-layer, recent reports have evidenced a cross-breed itinerant and localized nature of the electronic excitations, similar to what is typically found in heavy fermion systems. Here, we put forward a new interpretation based on first-principles calculations which indicates a sizeable charge transfer of electrons (0.4-0.6 e) from 1T to 1H layers at an elevated interlayer distance. We accurately quantify the strength of the interlayer hybridization which allows us to unambiguously determine that the system is much closer to a doped Mott insulator than to a heavy fermion scenario. Ta-based heterolayers provide therefore a new ground for quantum-materials engineering in the regime of heavily doped Mott insulators hybridized with metallic states at a van der Waals distance.

Complex ligand adsorption on 3D atomic surfaces of synthesized nanoparticles investigated by machine-learning accelerated ab initio calculation.

Nanoparticle surfaces are passivated by surface-bound ligands, and their adsorption on synthesized nanoparticles is complicated because of the intricate and low-symmetry surface structures. Thus, it is challenging to precisely investigate ligand adsorption on synthesized nanoparticles. Here, we applied machine-learning-accelerated ab initio calculation to experimentally resolved 3D atomic structures of Pt nanoparticles to analyze the complex adsorption behavior of polyvinylpyrrolidone (PVP) ligands on synthesized nanoparticles. Different angular configurations of large-sized ligands are thoroughly investigated to understand the adsorption behavior on various surface-exposed atoms with intrinsic low-symmetry. It is revealed that the ligand binding energy (Eads) of the large-sized ligand shows a weak positive relationship with the generalized coordination number . This is because the strong positive relationship of short-range direct bonding (Ebind) is attenuated by the negative relationship of long-range van der Waals interaction (EvdW). In addition, it is demonstrated that the PVP ligands prefer to adsorb where the long-range vdW interaction with the surrounding surface structure is maximized. Our results highlight the significant contribution of vdW interactions and the importance of the local geometry of surface atoms to the adsorption behavior of large-sized ligands on synthesized nanoparticle surfaces.

Ultrasensitive N-Channel Graphene Gas Sensors by Nondestructive Molecular Doping.

Sensitive and selective detection of target gases is the ultimate goal for commercialization of graphene gas sensors. Here, ultrasensitive n-channel graphene gas sensors were developed by using n-doped graphene with ethylene amines. The exposure of the n-doped graphene to oxidizing gases such as NO2 leads to a current decrease that depends strongly on the number of amine functional groups in various types of ethylene amines. Graphene doped with diethylenetriamine (DETA) exhibits the highest response, recovery, and long-term sensing stability to NO2, with an average detection limit of 0.83 parts per quadrillion (ppq, 10-15), due to the attractive electrostatic interaction between electron-rich graphene and electron-deficient NO2. Our first-principles calculation supported a preferential adsorption of NO2 on n-doped graphene. In addition, gas molecules on the n-channel graphene provide charged impurities, thereby intensifying the current decrease for an excellent response to oxidizing gases such as NO2 or SO2. On the contrary, absence of such a strong interaction between NH3 and DETA-doped graphene and combined effects of current increase by n-doping and mobility decrease by charged impurities result in a completely no response to NH3. Because the n-channel is easily induced by a top-molecular dopant, a flexible graphene sensor with outstanding NO2 detection capability was successfully fabricated on plastic without vertical stacks of gate-electrode and gate-dielectric. Our gate-free graphene gas sensors enabled by nondestructive molecular n-doping could be used for the selective detection of subppq-level NO2 in a gas mixture with reducing gases.

Conversion of CO2 into Formic Acid on Transition Metal-Porphyrin-like Graphene: First Principles Calculations.

Recently, transition metal (TM)-porphyrin-like graphene has been predicted to be a promising material for CO2 capturing under favorable conditions. Such materials can capture CO2 at 300 K and release it at 450 K. However, the captured CO2 gas is mostly stored in oceans. With the aid of first principles calculations, we herein propose a method in which the captured CO2 is converted into an environmentally friendly product, formic acid. Addition of H2 to CO2 molecules adsorbed on Sc- and Ti-porphyrin-like graphene was found to catalyze this conversion. We also performed nudged elastic band calculations and thermodynamic analysis using the first-order Polanyi-Wigner equation and equilibrium statistical mechanics to investigate the chemical reactions involved in this conversion. In addition, we performed Bader charge analysis to obtain insights into the mechanism of charge transfer and adsorption throughout the conversion. Our study presents a novel method in which the captured CO2 is treated by converting it into an environmentally friendly product. Since this method does not require CO2 storage, it is expected to be an effective strategy to manage the rising CO2 level in the environment.

Unidirectional Alignment of AgCN Microwires on Distorted Transition Metal Dichalcogenide Crystals.

Van der Waals epitaxy on the surface of two-dimensional (2D) layered crystals has gained significant research interest for the assembly of well-ordered nanostructures and fabrication of vertical heterostructures based on 2D crystals. Although van der Waals epitaxial assembly on the hexagonal phase of transition metal dichalcogenides (TMDCs) has been relatively well characterized, a comparable study on the distorted octahedral phase (1T' or Td) of TMDCs is largely lacking. Here, we investigate the assembly behavior of one-dimensional (1D) AgCN microwires on various distorted TMDC crystals, namely 1T'-MoTe2, Td-WTe2, and 1T'-ReS2. The unidirectional alignment of AgCN chains is observed on these crystals, reflecting the symmetry of underlying distorted TMDCs. Polarized Raman spectroscopy and transmission electron microscopy directly confirm that AgCN chains display the remarkable alignment behavior along the distorted chain directions of underlying TMDCs. The observed unidirectional assembly behavior can be attributed to the favorable adsorption configurations of 1D chains along the substrate distortion, which is supported by our theoretical calculations and observation of similar assembly behavior from different cyanide chains. The aligned AgCN microwires can be harnessed as facile markers to identify polymorphs and crystal orientations of TMDCs.

Critical differences in 3D atomic structure of individual ligand-protected nanocrystals in solution.

Precise three-dimensional (3D) atomic structure determination of individual nanocrystals is a prerequisite for understanding and predicting their physical properties. Nanocrystals from the same synthesis batch display what are often presumed to be small but possibly important differences in size, lattice distortions, and defects, which can only be understood by structural characterization with high spatial 3D resolution. We solved the structures of individual colloidal platinum nanocrystals by developing atomic-resolution 3D liquid-cell electron microscopy to reveal critical intrinsic heterogeneity of ligand-protected platinum nanocrystals in solution, including structural degeneracies, lattice parameter deviations, internal defects, and strain. These differences in structure lead to substantial contributions to free energies, consequential enough that they must be considered in any discussion of fundamental nanocrystal properties or applications.

Theoretical investigation of the vertical dielectric screening dependence on defects for few-layered van der Waals materials.

First-principle calculations were employed to analyze the effects induced by vacancies of molybdenum (Mo) and sulfur (S) on the dielectric properties of few-layered MoS2. We explored the combined effects of vacancies and dipole interactions on the dielectric properties of few-layered MoS2. In the presence of dielectric screening, we investigated uniformly distributed Mo and S vacancies, and then considered the case of concentrated vacancies. Our results show that the dielectric screening remarkably depends on the distribution of vacancies owing to the polarization induced by the vacancies and on the interlayer distances. This conclusion was validated for a wide range of wide-gap semiconductors with different positions and distributions of vacancies, providing an effective and reliable method for calculating and predicting electrostatic screening of dimensionally reduced materials. We further provided a method for engineering the dielectric constant by changing the interlayer distance, tuning the number of vacancies and the distribution of vacancies in few-layered van der Waals materials for their application in nanodevices and supercapacitors.

Control of CO2 Capture Process on Transition-Metal-Porphyrin-like Graphene with Mechanical Strain.

Nanomaterials, such as zeolites and metal-organic frameworks, have been studied for CO2 capture and sequestration. However, this application of nanomaterials has been limited largely due to their poor selectivity for flue gases as well as low capture capacity under low pressures. The first-principle density-functional theory calculations for porphyrin-like graphene decorated with a transition metal were performed to investigate the effects of mechanical strain on its CO2 capture capacity. We found that Sc- and V-decorated porphyrin-like graphenes could capture CO2 molecules selectively from gaseous mixtures under low CO2 pressure with compressive strain and release them with tensional strain at room temperatures. The CO2 binding to these transition metals was understood to be mostly due to the Dewar interaction involving hybridization of the metal d orbitals with π orbitals of CO2. These results elucidate a novel approach to the CO2 capture process with the application of the mechanical strain to nanomaterials.

Corrigendum: High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide.

This corrects the article DOI: 10.1038/srep21788.

Wedge energy bands of monolayer black phosphorus: a first-principles study.

On the basis of first-principles calculations, we present intriguing electronic properties of halogen-striped functionalized monolayer black phosphorus. The halogen-striped monolayer black phosphorus is found to have a wedge energy band with the energy-momentum relation of [Formula: see text] when the stripe-stripe distance is smaller than ~40 Å. Our tight-binding study shows that the wedge energy band occurs when 2-atom basis 1D lattices are periodically repeated aligned with each other in a 2D lattice. We also discuss the possible applications of this wedge energy band in electron supercollimation with high mobility or severely anisotropic electronic transport, which can be used for the development of optics-like nano-electronics.

Direct Observation of the Collision of Single Pt Nanoparticles onto Single-Crystalline Gold Nanowire Electrodes.

We observed the collision of single Pt nanoparticles (NPs) onto an Au nanowire (NW) electrode by using electrocatalytic amplification. Previously, such observations had typically been performed by using a microscale disk-type ultramicroelectrode (UME). The use of a NW electrode decreased the background noise current and provided a shielding effect, owing to adsorption of the NPs onto the insulating sheath. Therefore, the transient current signal that was caused by the collision of single NPs could be more clearly distinguished from the background current by using a NW electrode instead of a UME. Furthermore, the use of a NW electrode increased the collisional frequency and the magnitude of the transient current signal. The experimental data were analyzed by using a theoretical model and a random walk simulation model.

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide.

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10(-3) bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.