Abnormal Silicon Etching Behaviors in Nanometer-Sized Channels.

Modern semiconductor fabrication is challenged by difficulties in overcoming physical and chemical constraints. A major challenge is the wet etching of dummy gate silicon, which involves the removal of materials inside confined spaces of a few nanometers. These chemical processes are significantly different in the nanoscale and bulk. Previously, electrical double-layer formation, bubble entrapment, poor wettability, and insoluble intermediate precipitation have been proposed. However, the exact suppression mechanisms remain unclear due to the lack of direct observation methods. Herein, we investigate limiting factors for the etching kinetics of silicon with tetramethylammonium hydroxide at the nanoscale by using liquid-phase transmission electron microscopy, three-dimensional electron tomography, and first-principles calculations. We reveal suppressed chemical reactions, unstripping phenomena, and stochastic etching behaviors that have never been observed on a macroscopic scale. We expect that solutions can be suggested from this comprehensive insight into the scale-dependent limiting factors of fabrication.

Electrocatalytic Activation in ReSe2-VSe2 Alloy Nanosheets to Boost Water-Splitting Hydrogen Evolution Reaction.

It is challenging to control the electronic structure of 2D transition metal dichalcogenides (TMD) for extended applications in renewable energy devices. Here, ReSe2-VSe2 (Re1- xVxSe2) alloy nanosheets over the whole composition range via a colloidal reaction is synthesized. Increasing x makes the nanosheets more metallic and induces a 1T″-to-1T phase transition at x = 0.5-0.6. Compared to the MoSe2-VSe2 and WSe2-VSe2 alloy nanosheets, ReSe2 and VSe2 are mixed more homogeneously at the atomic scale. The alloy nanosheets at x = 0.1-0.7 exhibit an enhanced electrocatalytic activity toward acidic hydrogen evolution reaction (HER). In situ X-ray absorption fine structure measurements reveal that alloying caused the Re and V atoms to be synergically more active in the HER. Gibbs free energy (ΔGH*) and density of state calculations confirm that alloying and Se vacancies effectively activate the metal sites toward HER. The composition dependence of HER performance is explained by homogenous atomic mixing with the increased Se vacancies. The study provides a strategy for designing new TMD alloy nanosheets with enhanced catalytic activity.

2H-2M Phase Control of WSe2 Nanosheets by Se Enrichment Toward Enhanced Electrocatalytic Hydrogen Evolution Reaction.

The phase control of transition metal dichalcogenides (TMDs) is an intriguing approach for tuning the electronic structure toward extensive applications. In this study, WSe2 nanosheets synthesized via a colloidal reaction exhibit a phase conversion from semiconducting 2H to metallic 2M under Se-rich growth conditions (i.e., increasing the concentration of Se precursor or lowering the growth temperature). High-resolution scanning transmission electron microscopy images are used to identify the stacking sequence of the 2M phase, which is distinctive from that of the 1T' phase. First-principles calculations employing various Se-rich models (intercalation and substitution) indicated that Se enrichment induces conversion to the 2M phase. The 2M phase WSe2 nanosheets with the Se excess exhibited enhanced electrocatalytic performance in the hydrogen evolution reaction (HER). In situ X-ray absorption fine structure studies suggested that the excess Se atoms in the 2M phase WSe2 enhanced the HER catalytic activity, which is supported by the Gibbs free energy (ΔGH* ) of H adsorption and the Fermi abundance function. These results provide an appealing strategy for phase control of TMD catalysts.

Ultrafast Nucleation Reverses Dissolution of Transition Metal Ions for Robust Aqueous Batteries.

The dissolution of transition metal ions causes the notorious peeling of active substances and attenuates electrochemical capacity. Frustrated by the ceaseless task of pushing a boulder up a mountain, Sisyphus of the Greek myth yearned for a treasure to be unearthed that could bolster his efforts. Inspirationally, by using ferricyanide ions (Fe(CN)63-) in an electrolyte as a driving force and taking advantage of the fast nucleation rate of copper hexacyanoferrate (CuHCF), we successfully reversed the dissolution of Fe and Cu ions that typically occurs during cycling. The capacity retention increased from 5.7% to 99.4% at 0.5 A g-1 after 10,000 cycles, and extreme stability of 99.8% at 1 A g-1 after 40,000 cycles was achieved. Fe(CN)63- enables atom-by-atom substitution during the electrochemical process, enhancing conductivity and reducing volume change. Moreover, we demonstrate that this approach is applicable to various aqueous batteries (i.e., NH4+, Li+, Na+, K+, Mg2+, Ca2+, and Al3+).

Composition-Tuned (MoWV)Se2 Ternary Alloy Nanosheets as Excellent Hydrogen Evolution Reaction Electrocatalysts.

Ternary alloying of transition metal dichalcogenides (TMDs) has the potential for altering the electronic structure of materials to suit electrochemical applications. Herein, we synthesized (MoWV)Se2 nanosheets at various compositions via a colloidal reaction. The mole fraction of V atoms (xV) was successfully increased up to 0.8, producing a metallic phase that is highly durable against hydration. Furthermore, we synthesized (MoW)Se2 nanosheets over the entire composition range. The atomic mixing of the ternary alloys is more random than that of the constitutional binary alloys, as supported by first-principles calculations. Compared to binary alloying, ternary alloying more effectively enhanced the electrocatalytic activity for acidic hydrogen evolution reaction (HER). The HER performance increased upon increasing xV to 0.44, and thereafter, it declined at higher xV primarily owing to surface oxidation. The analysis of Gibbs free energy for H adsorption revealed that ternary alloying strongly activates the basal plane for the HER. VSe2 contains numerous sites favorable for H adsorption, facilitating the composition-dependent HER. These results provide a pioneering strategy for designing multicomponent TMD catalysts that maximize the advantages of each component.

Full Composition Tuning of W1-xNbxSe2 Alloy Nanosheets to Promote the Electrocatalytic Hydrogen Evolution Reaction.

Composition modulation of transition metal dichalcogenides is an effective way to engineer their crystal/electronic structures for expanded applications. Here, fully composition-tuned W1-xNbxSe2 alloy nanosheets were produced via colloidal synthesis. These nanosheets ultimately exhibited a notable transition between WSe2 and NbSe2 hexagonal phases at x = 0.6. As x approaches 0.6, point doping is converted into cluster doping and eventually separated domains of WSe2 and NbSe2. Extensive density functional theory calculations predicted the composition-dependent crystal structures and phase transitions, consistently with the experiments. The electrocatalytic activity for the hydrogen evolution reaction (HER) in acidic electrolyte was significantly enhanced at x = 0.2, which was linked with the d-band center. The Gibbs free energy for the H adsorption at various basal and edge sites supported the enhanced HER performance of the metallic alloy nanosheets. We suggested that the dispersed doping structures of Nb atoms resulted in the best HER performance. Our findings highlight the significance of composition tuning in enhancing the catalytic activity of alloys.

WSe2-VSe2 Alloyed Nanosheets to Enhance the Catalytic Performance of Hydrogen Evolution Reaction.

Tuning the electronic structures of transition metal dichalcogenides (TMD) is essential for their implementation in next-generation energy technologies. In this study, we synthesized composition-tuned WSe2-VSe2 (W1-xVxSe2, x = 0-1) alloyed nanosheets using a colloidal reaction. Alloying the semiconducting WSe2 with VSe2 converts the material into a metallic one, followed by a 2H-to-1T phase transition at x = 0.7. Over a wide composition range, WSe2 and VSe2 are atomically immiscible and form separate ordered domains. The miscible alloy at x = 0.1 displayed enhanced electrocatalytic activity toward the hydrogen evolution reaction (HER) in an acidic electrolyte. This trend was correlated with the d-band center via a volcano-type relationship. Spin-polarized density functional theory calculations consistently predicted the atomic immiscibility, which became more significant at the 2H-1T phase transition composition. The Gibbs free energy of H adsorption on the basal planes (Se or hole sites) and the activation barriers along the Volmer-Heyrovsky reaction pathway supported the enhanced HER performance of the alloy phase, suggesting that the dispersed V-doped structures were responsible for the best HER catalytic activity. Our study demonstrates how the atomic structure of TMD alloy nanosheets plays a crucial role in enhancing catalytic activity.

MoSe2 -VSe2 -NbSe2 Ternary Alloy Nanosheets to Boost Electrocatalytic Hydrogen Evolution Reaction.

Alloying of transition metal dichalcogenides (TMDs) is a pioneering method for engineering electronic structures with expanded applications. In this study, MoSe2 -VSe2 -NbSe2 ternary alloy nanosheets are synthesized via a colloidal reaction. The composition is successfully tuned over a wide range to adjust the 2H-1T phase transition. The alloy nanosheets consist of miscible atomic structures at all compositions, which is distinct from immiscible binary alloys. Compared to each binary alloy, the ternary alloys display higher electrocatalytic activity toward the hydrogen evolution reaction (HER) in an acidic electrolyte. The HER performance exhibits a volcano-type composition dependence, which is correlated with the experimental d-band center (εd ). Spin-polarized density functional theory (DFT) calculations consistently predict the homogenous atomic distributions. The Gibbs free energy of H adsorption (ΔGH* ) and the activation barrier (Ea ) support that miscible ternary alloying greatly enhances the HER performance.

Polytypic Phase Transition of Nb1-xVxSe2 via Colloidal Synthesis and Their Catalytic Activity toward Hydrogen Evolution Reaction.

Polytypes of two-dimensional transition metal dichalcogenide can extend the architecture and application of nanostructures. Herein, Nb1-xVxSe2 alloy nanosheets in the full composition range (x) were synthesized by a colloidal reaction. At x = 0.1-0.3, a phase transition occurred from various hexagonal (three 2H and one 4H types) phase NbSe2 to an atomically homogeneous 1T phase VSe2. Density functional theory calculations also revealed a polytypic phase transition at x = 0.3, which was shifted close to 0 in the presence of Se vacancies. Furthermore, the calculations validate favorable formation of Se vacancies at the phase transition. The sample at x = 0.3 exhibited enhanced electrocatalytic activity toward the hydrogen evolution reaction (HER) in 0.5 M H2SO4. The Gibbs free energy indicates that the catalytic HER performance is correlated with the active Se vacancy sites of polytypic structures.

Non-Equilibrium Sodiation Pathway of CuSbS2.

Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS2, but also investigate its nonequilibrium sodiation pathway employing in-/ex situ transmission electron microscopy, in situ X-ray diffraction, and density functional theory calculations. Our finding provides valuable insights on sodium storage into ternary metal sulfide including an alloying element.

Phase-Transition Mo1-xVxSe2 Alloy Nanosheets with Rich V-Se Vacancies and Their Enhanced Catalytic Performance of Hydrogen Evolution Reaction.

Alloys of transition-metal dichalcogenide can display distinctive phase evolution because of their two-dimensional structures. Herein, we report the colloidal synthesis of Mo1-xVxSe2 alloy nanosheets with full composition tuning. Alloying led to a phase transition at x = 0.7 from the semiconducting 2H phase MoSe2 to the metallic 1T phase VSe2. It also produced significant V and Se vacancies, which became the richest in the 2H phase at x = 0.3-0.5. Extensive spin-polarized density functional theory calculations consistently predicted the 2H-1T phase transition at x = 0.7, in agreement with the experimental results. The vacancy formation energy also supports the formation of V and Se vacancies. Alloying in the 2H phase enhanced the electrocatalytic performance toward hydrogen evolution reaction (HER) at x = 0.3 (in 0.5 M H2SO4) or 0.4 (in 1 M KOH). The Gibbs free energy along the HER pathway indicates that this maximum performance is due to the highest concentration of active V and Se vacancy sites.

Preparation of a polymer nanocomposite via the polymerization of pyrrole : biphenyldisulfonic acid : pyrrole as a two-monomer-connected precursor on MoS2 for electrochemical energy storage.

We prepared a poly(pyrrole : biphenyldisulfonic acid : pyrrole (Py:BPDSA:Py)) nanocomposite of molybdenum disulfide (MoS2), P(Py:BPDSA:Py)-MoS2, with high crystallinity. The composite is synthesized by oxidative polymerization of Py:BPDSA:Py as a two-monomer-connected precursor (TMCP) linked by ionic bonding on a molybdenum disulfide (MoS2) monolayer. The chemical, structural and morphological characterization of this composite is confirmed by Raman spectroscopy, FT-IR, X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (EELS), and scanning electron microscopy (SEM). The crystal structure is analysed by X-ray diffraction (XRD) and high-voltage electron microscopy (HVEM), which shows a face-centered cubic (FCC) crystal structure for the composite. Nitrogen adsorption-desorption isotherms show an improved specific surface area (91.3 m2 g-1). The electrochemical properties of the composite with a unique crystal structure and a large specific surface area are analysed through cyclic voltammetry (CV), which shows a specific capacitance of 681 F g-1 demonstrating that the composite can be used as an efficient electrode active material for electrochemical energy storage systems.

Ruthenium Nanoparticles on Cobalt-Doped 1T' Phase MoS2 Nanosheets for Overall Water Splitting.

2D MoS2 nanostructures have recently attracted considerable attention because of their outstanding electrocatalytic properties. The synthesis of unique Co-Ru-MoS2 hybrid nanosheets with excellent catalytic activity toward overall water splitting in alkaline solution is reported. 1T' phase MoS2 nanosheets are doped homogeneously with Co atoms and decorated with Ru nanoparticles. The catalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is characterized by low overpotentials of 52 and 308 mV at 10 mA cm-2 and Tafel slopes of 55 and 50 mV decade-1 in 1.0 m KOH, respectively. Analysis of X-ray photoelectron and absorption spectra of the catalysts show that the MoS2 well retained its metallic 1T' phase, which guarantees good electrical conductivity during the reaction. The Gibbs free energy calculation for the reaction pathway in alkaline electrolyte confirms that the Ru nanoparticles on the Co-doped MoS2 greatly enhance the HER activity. Water adsorption and dissociation take place favorably on the Ru, and the doped Co further catalyzes HER by making the reaction intermediates more favorable. The high OER performance is attributed to the catalytically active RuO2 nanoparticles that are produced via oxidation of Ru nanoparticles.

Thermally Activated Upconversion Near-Infrared Photoluminescence from Carbon Dots Synthesized via Microwave Assisted Exfoliation.

Upconversion near-infrared (NIR) fluorescent carbon dots (CDs) are important for imaging applications. Herein, thermally activated upconversion photoluminescence (UCPL) in the NIR region, with an emission peak at 784 nm, which appears under 808 nm continuous-wave laser excitation, are realized in the NIR absorbing/emissive CDs (NIR-CDs). The NIR-CDs are synthesized by microwave-assisted exfoliation of red emissive CDs in dimethylformamide, and feature single or few-layered graphene-like cores. This structure provides an enhanced contact area of the graphene-like plates in the core with the electron-acceptor carbonyl groups in dimethylformamide, which contributes to the main NIR absorption band peaked at 724 nm and a tail band in 800-850 nm. Temperature-dependent photoluminescence spectra and transient absorption spectra confirm that the UCPL of NIR-CDs is due to the thermally activated electron transitions in the excited state, rather than the multiphoton absorption process. Temperature dependent upconversion NIR luminescence imaging is demonstrated for NIR-CDs embedded in a polyvinyl pyrrolidone film, and the NIR upconversion luminescence imaging in vivo using NIR-CDs in a mouse model is accomplished.

Chemically Synthesized Carbon Nanorods with Dual Polarized Emission.

We realized the synthesis of carbon nanorods-monodisperse colloidal particles with a length of 50 nm and a width of 20 nm-which can be considered an addition to the family of light-emitting carbon-based nanostructures. Their anisotropic shape is determined by the use of the surfactant aminopropylisobutyl polyhedral oligomeric silsesquioxane, and their optical properties originate from domains of polycyclic aromatic hydrocarbons incorporated within an inorganic framework. The nanorods show dual polarized emission with a quantum yield of 15-20% and emission anisotropy of ∼0.3, which changes from blue (460 nm) to yellow (565 nm) depending on the excitation wavelength. These carbon nanorods expand the range of light-emitting carbon nanomaterials available for optoelectronic and biolabeling applications.

Growth of close-packed crystalline polypyrrole on graphene oxide via in situ polymerization of two-monomer-connected precursors.

Synthesis of a two-dimensional (2D) highly crystalline composite, P(Py:BPDSA:Py)-GO, from the growth of a close-packed polymer crystal, P(Py:BPDSA:Py), on graphene oxide (GO) sheets via in situ polymerization of two-monomer-connected precursors (TMCPs, Py:BPDSA:Py), in which two pyrrole (Py) molecules are linked through a connector (4,4'-biphenyldisulfonic acid) (BPDSA), is reported. When the TMCP is polymerized on GO, it leads to an exceptionally ordered structure determined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies. X-ray crystallography of the composite shows crystalline peaks with d spacings in the [100] direction. Transmission electron microscopy (TEM) analysis indicates that the composite has a face-centered cubic (FCC) crystal structure. Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) show that this composite with a well-defined nanostructure was successfully synthesized. Nitrogen adsorption-desorption isotherms show that this composite, P(Py:BPDSA:Py)-GO, has an improved specific surface area (71 m2 g-1) compared to that of P(Py:BPDSA:Py) (3.1 m2 g-1). The electrochemical properties of the composite studied by cyclic voltammetry indicates a specific capacitance of 480 F g-1 without an additional conducting material such as carbon black, suggesting its use as a pseudocapacitor.

Integrating Catalysis of Methane Decomposition and Electrocatalytic Hydrogen Evolution with Ni/CeO2 for Improved Hydrogen Production Efficiency.

Ni/CeO2 enables either methane decomposition or water electrolysis for pure hydrogen production. Ni/CeO2 , prepared by a sol-gel method with only one heat treatment step, was used to catalyze methane decomposition for the generation of H2 . The solid byproduct, Ni/CeO2 /carbon nanotube (CNT), was further employed as an electrocatalyst in the hydrogen evolution reaction (HER) for H2 production. The Ni/CeO2 catalyst exhibits excellent activity for methane decomposition because CeO2 prevents carbon encapsulation of Ni nanoparticles during the preparation process and forms a special metal-support interface with Ni. The derived CNTs act as antenna to improve conductivity and promote the dispersion of agglomerated Ni/CeO2 . In addition, they provide H2 diffusion paths and prevent Ni/CeO2 from peeling off the HER electrode. Although long-term methane decomposition reduces the HER activity of Ni/CeO2 /CNTs (owing to degradation of the delicate Ni/CeO2 interface), the tunable nature of the synthesis makes this an attractive sustainable approach to synthesize future high-performance materials.

Interfacial CoOx Layers on TiO2 as an Efficient Catalyst for Solvent-Free Aerobic Oxidation of Hydrocarbons.

Construction of efficient interfaces to improve the performance of supported metal catalysts is a challenging but effective technique. A newly synthesized catalyst with layered cobalt oxide on the surface of titania (layer-CoOx /TiO2 ) is highly selective towards the aerobic oxidation of C-H bonds in a series of hydrocarbons under sustainable conditions. The layer-CoOx /TiO2 easily outperforms the state-of-the-art noble metal catalysts and homogeneous cobalt salts used in industry. In-depth structural and functional characterization reveal that the layer-CoOx /TiO2 readily reacts with O2 for the adsorption and activation of C-H bonds. The layered structure of CoOx can maximize the interfacial effect of CoOx /TiO2 leading to a good performance for the oxidation of C-H bonds.

Analysis of nano-crystals: Evaluation of heavy metal-embedded biological specimen by high voltage electron microscopy.

Heavy metal compounds are adsorbed onto biological specimen in order to enhance the contrast as well as to preserve the structural features of the specimen against electron beam-induced radiation damage. In particular, in combination with computational image processing, negative staining is widely used for structural analysis of protein complexes to moderate resolutions. Image analysis of negatively stained biological specimen is known to suffer from limited achievable resolution due to dehydration and large grain size of staining molecules although the extent of such effect remains somewhat dubious. Stain molecules exist as grains under electron beam. However, clear observation of the crystalline nature of the grains and their association with biological specimen has not been thoroughly demonstrated. In this study, we attempted high-resolution TEM (HRTEM) using high voltage electron microscopy and electron crystallography analysis for the detailed characterization of negatively stained biological specimen, focusing on physical state and chemical composition of the stain molecules. The electron crystallography analysis allowed for the identification of the crystal constituents of widely used stains, hence revealing the chemical nature and the morphology of the stain molecules at specimen level. This study re-evaluated generally accepted notions on negative staining, and may help correctly interpreting the structural analysis of stained biological specimen.

Nitrogen-rich 1T'-MoS2 layered nanostructures using alkyl amines for high catalytic performance toward hydrogen evolution.

The imminent global energy crisis and current environmental issues have stimulated considerable research on high-performance catalysts for sustainable hydrogen energy generation. Two-dimensional layered MoS2 has recently drawn worldwide attention because of its excellent catalytic properties for the hydrogen evolution reaction (HER). In the present work, we prepared nitrogen (N)-rich 1T' (distorted 1T) phase MoS2 layered nanostructures using different alkyl amines with 1-4 nitrogen atoms (methylamine, ethylenediamine, diethylenetriamine, and triethylenetetramine) as intercalants. The amine molecules intercalate at 10 atomic%, and simultaneously supply the N atoms that substitute the S atoms to produce the N-doped MoS2, whose composition is MoS2(1-x)Nx, where x = 0.1-0.26. MoS2 prepared with amines having more N atoms has enhanced catalytic HER performance: a Tafel slope of 36 mV dec-1 and 10 mA cm-2 at -160 mV (vs. RHE). First-principles calculations showed that the amine intercalation and N doping increase the density of states near the Fermi level in a narrow range and bring about an effective overlap of the dz2(Mo), pz(S), and pz(N) states. These factors in turn increase the carrier (electron) concentration and mobility for improved HER. The calculation also predicted that the most active site is S vacancies. The present work illustrates how the HER catalytic performance of 1T' phase MoS2 can be effectively controlled by the amine molecules.