High yield and wide lateral size growth of α-Mo2C: exploring the boundaries of CVD growth of bare MXene analogues.

Synthesis of Mo2C bare MXenes, without surface terminations groups, via chemical vapor deposition (CVD) on metal foils is scientifically a very intriguing crystal growth process, and there are still challenges and limited fundamental understanding to overcome to obtain high yield and wide crystal size lateral growth. Achieving large area coverage via direct growth is scientifically vital to utilize the full potential of their unique properties in different applications. In this study, we sought to expand the boundaries of the current CVD growth approach for Mo2C MXenes and gain insights into the possibilities and limitations of large area growth, with a particular focus on controlling Mo concentration. We report a facile modification of their typical CVD growth protocol and show its influence on the Mo2C synthesis, with growth times spanning up to 3 h. Specifically, prior to initiating the CVD growth process, we introduced a holding step in temperature at 1095 °C. This proved to be beneficial in increasing the Mo concentration on the liquid Cu growth surface. We achieved an average Mo2C crystals coverage of approximately 50% of the growth substrate area, increased tendency of coalescence and merging of individual flakes, and lateral flake sizes up to 170µm wide. To gain deeper understanding into their CVD growth behavior, we conducted a systematic investigation of the effect of several factors, including (i) a holding step time on Mo diffusion rate through molten Cu, (ii) the Cu foil thickness over the Mo foil, and (iii) the CVD growth time. Phase, chemical and microstructural characterization by x-ray diffraction, x-ray photon spectroscopy, SEM and scanning/transmission electron microscopy revealed that the grown crystals are single phaseα-Mo2C. Furthermore, insights gained from this study sheds light on crucial factors and inherent limitations that are essential to consider and may help guide future research progress in CVD growth of bare MXenes.

Eliminating Graphite Exfoliation with an Artificial Solid Electrolyte Interphase for Stable Lithium-Ion Batteries.

Although graphite materials with desirable comprehensive properties dominate the anode market of commercial lithium-ion batteries (LIBs), their low capacity during fast charging precludes further commercialization. In the present work, natural graphite (G) is reported not only to suffer from low capacity during fast charging, but also from charge failure after many charging cycles. Using different characterization techniques, severe graphite exfoliation, and continuously increasing solid electrolyte interphase (SEI) are demonstrated as reasons for the failure of G samples. An ultrathin artificial SEI is proposed, addressing these problems effectively and ensuring extremely stable operation of the graphite anode, with a capacity retention of ≈97.5% after 400 cycles at 1 C. Such an artificial SEI modification strategy provides a universal approach to tailoring and designing better anode materials for next-generation LIBs with high energy densities.

Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation.

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C-N-C, [double bond, length as m-dash]NH or -NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4.

2D Intrinsic Ferromagnetic MnP Single Crystals.

2D intrinsic ferromagnetic materials are highly anticipated in spintronic devices due to their coveted 2D limited magnetism. However, 2D non-layered intrinsic ferromagnets have received sporadic attention, which is largely attributed to the fact that their synthesis is still a great challenge. Significantly, manganese phosphide (MnP) is a promising non-layered intrinsic ferromagnet with excellent properties. Herein, high-quality 2D MnP single crystals formed over liquid metal tin (Sn) is demonstrated through a facile chemical vapor deposition technique. The introduction of liquid metal Sn provides a fertile ground for the growth of 2D MnP single crystals. Interestingly, 2D MnP single crystals maintain their intrinsic ferromagnetism and exhibit a Curie temperature above room temperature. The research enriches the diversity of 2D intrinsic ferromagnetic materials, opening up opportunities for further exploration of their unique properties and rich applications.

In Situ N-Doped Graphene and Mo Nanoribbon Formation from Mo2 Ti2 C3 MXene Monolayers.

Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2 Ti2 C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2 Ti2 C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2 Ti2 C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2 Ti2 C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials.

Applications of 2D MXenes in energy conversion and storage systems.

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Effect of Milling and Annealing on Carbon-Silver System.

Mechanical treatment of graphite silver mixture followed by heat treatment showed morphology and structure changes of both components. Silver is being distributed over graphite flakes randomly with higher concentration on the edges and nanometric size, which was observed using scanning and transmission electron microscopy. The annealing temperature 1300 °C is higher than melting temperature of silver (961.8 °C) and base on phase diagram C-Ag (C. L. Chen, et al., Appl. Phys. Lett. 96, 253104 (2010).) silver is being transferred from liquid phase to solid phase at rapid cooling, which is giving various crystallinity.

In Situ Electron Driven Carbon Nanopillar-Fullerene Transformation through Cr Atom Mediation.

The promise of sp2 nanomaterials remains immense, and ways to strategically combine and manipulate these nanostructures will further enhance their potential as well as advance nanotechnology as a whole. The scale of these structures requires precision at the atomic scale. In this sense electron microscopes are attractive as they offer both atomic imaging and a means to structurally modify structures. Here we show how Cr atoms can be used as physical linkers to connect carbon nanotubes and fullerenes to graphene. Crucially, while under electron irradiation, the Cr atoms can drive transformations such as catalytic healing of a hole in graphene with simultaneous transformation of a single wall carbon nanotube into a fullerene. The atomic resolution of the electron microscopy along with density functional theory based total energy calculations provide insight into the dynamic transformations of Cr atom linkers. The work augments the potential of transmission electron microscopes as nanolaboratories.

Stranski-Krastanov and Volmer-Weber CVD Growth Regimes To Control the Stacking Order in Bilayer Graphene.

Aside from unusual properties of monolayer graphene, bilayer has been shown to have even more interesting physics, in particular allowing bandgap opening with dual gating for proper interlayer symmetry. Such properties, promising for device applications, ignited significant interest in understanding and controlling the growth of bilayer graphene. Here we systematically investigate a broad set of flow rates and relative gas ratio of CH4 to H2 in atmospheric pressure chemical vapor deposition of multilayered graphene. Two very different growth windows are identified. For relatively high CH4 to H2 ratios, graphene growth is relatively rapid with an initial first full layer forming in seconds upon which new graphene flakes nucleate then grow on top of the first layer. The stacking of these flakes versus the initial graphene layer is mostly turbostratic. This growth mode can be likened to Stranski-Krastanov growth. With relatively low CH4 to H2 ratios, growth rates are reduced due to a lower carbon supply rate. In addition bi-, tri-, and few-layer flakes form directly over the Cu substrate as individual islands. Etching studies show that in this growth mode subsequent layers form beneath the first layer presumably through carbon radical intercalation. This growth mode is similar to that found with Volmer-Weber growth and was shown to produce highly oriented AB-stacked materials. These systematic studies provide new insight into bilayer graphene formation and define the synthetic range where gapped bilayer graphene can be reliably produced.

Scalable Seashell-Based Chemical Vapor Deposition Growth of Three-Dimensional Graphene Foams for Oil-Water Separation.

A seashell-based CVD technique for preparing three-dimensional (3D) graphene foams is reported. The graphene sheets in thus-obtained foams are seamlessly interconnected into a 3D flexible network, forming highly porous materials with negligible non-carbon impurities, ultralow density, and outstanding mechanical flexibility and electrical conductivity. These 3D graphene foams demonstrate a fast adsorption performance toward various oils and organic solvents, with adsorption capacity up to 250-fold weight gain. The present approach offers a practical route for scalable construction of 3D graphene foams for versatile applications such as energy storage and water remediation.

Direct Chemical Vapor Deposition-Derived Graphene Glasses Targeting Wide Ranged Applications.

Direct growth of graphene on traditional glasses is of great importance for various daily life applications. We report herein the catalyst-free atmospheric-pressure chemical vapor deposition approach to directly synthesizing large-area, uniform graphene films on solid glasses. The optical transparency and sheet resistance of such kinds of graphene glasses can be readily adjusted together with the experimentally tunable layer thickness of graphene. More significantly, these graphene glasses find a broad range of real applications by enabling the low-cost construction of heating devices, transparent electrodes, photocatalytic plates, and smart windows. With a practical scalability, the present work will stimulate various applications of transparent, electrically and thermally conductive graphene glasses in real-life scenarios.

Synthesis and toxicity characterization of carbon coated iron oxide nanoparticles with highly defined size distributions.

BACKGROUND: Iron oxide nanoparticles hold great promise for future biomedical applications. To this end numerous studies on iron oxide nanoparticles have been conducted. One aspect these studies reveal is that nanoparticle size and shape can trigger different cellular responses through endocytic pathways, cell viability and early apoptosis. However, systematic studies investigating the size dependence of iron oxide nanoparticles with highly defined diameters across multiple cells lines are not available yet. METHODS: Iron oxide nanoparticles with well-defined size distributions were prepared. All samples were thoroughly characterized and the cytotoxicity for four standard cell lines (HeLa Kyoto, human osteosarcoma (U2OS), mouse fibroblasts (NIH 3T3) and mouse macrophages (J7442)) where investigated. RESULTS: Our findings show that small differences in size distribution (ca. 10nm) of iron oxide nanoparticles do not influence cytotoxicity, while uptake is size dependent. Cytotoxicity is dose-dependent. Broad distributions of nanoparticles are more easily internalized as compared to the narrow distributions for two of the cell lines tested (HeLa Kyoto and mouse macrophages (J7442)). CONCLUSION: The data indicate that it is not feasible to probe changes in cytotoxicity within a small size range (10nm). However, TEM investigations of the nanoparticles indicate that cellular uptake is size dependent. GENERAL SIGNIFICANCE: The present work compares narrow and broad distributions for various samples of carbon-coated iron oxide nanoparticles. The data highlights that cells differentiate between nanoparticle sizes as indicated by differences in cellular uptake. This information provides valuable knowledge to better understand the interaction of nanoparticles and cells.

Direct Synthesis of Few-Layer Graphene on NaCl Crystals.

Chemical vapor deposition is used to synthesize few-layer graphene on micro crystalline sodium chloride (NaCl) powder. The water-soluble nature of NaCl makes it convenient to produce free standing graphene layers via a facile and low-cost approach. Unlike traditional metal-catalyzed or oxygen-aided growth, the micron-size NaCl crystal planes play an important role in the nucleation and growth of few-layer graphene. Moreover, the possibility of synthesizing cuboidal graphene is also demonstrated in the present approach for the first time. Raman spectroscopy, optical microscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy are used to evaluate the quality and structure of the few-layer graphene along with cuboidal graphene obtained in this process. The few-layer graphene synthesized using the present method has an adsorption ability for anionic and cationic dye molecules in water. The present synthesis method may pave a facile way for manufacturing few-layer graphene on a large scale.

Low voltage transmission electron microscopy of graphene.

The initial isolation of graphene in 2004 spawned massive interest in this two-dimensional pure sp(2) carbon structure due to its incredible electrical, optical, mechanical, and thermal effects. This in turn led to the rapid development of various characterization tools for graphene. Examples include Raman spectroscopy and scanning tunneling microscopy. However, the one tool with the greatest prowess for characterizing and studying graphene is the transmission electron microscope. State-of-the-art (scanning) transmission electron microscopes enable one to image graphene with atomic resolution, and also to conduct various other characterizations simultaneously. The advent of aberration correctors was timely in that it allowed transmission electron microscopes to operate with reduced acceleration voltages, so that damage to graphene is avoided while still providing atomic resolution. In this comprehensive review, a brief introduction is provided to the technical aspects of transmission electron microscopes relevant to graphene. The reader is then introduced to different specimen preparation techniques for graphene. The different characterization approaches in both transmission electron microscopy and scanning transmission electron microscopy are then discussed, along with the different aspects of electron diffraction and electron energy loss spectroscopy. The use of graphene for other electron microscopy approaches such as in-situ investigations is also presented.

Room temperature in situ growth of B/BOx nanowires and BOx nanotubes.

Despite significant advances in the synthesis of nanostructures, our understanding of the growth mechanisms of nanowires and nanotubes grown from catalyst particles remains limited. In this study we demonstrate a straightforward route to grow coaxial amorphous B/BOx nanowires and BOx nanotubes using gold catalyst particles inside a transmission electron microscope at room temperature without the need of any specialized or expensive accessories. Exceedingly high growth rates (over 7 µm/min) are found for the coaxial nanowires, and this is attributed to the highly efficient diffusion of B species along the surface of a nanowire by electrostatic repulsion. On the other hand the O species are shown to be relevant to activate the gold catalysts, and this can occur through volatile O species. The technique could be further developed to study the growth of other nanostructures and holds promise for the room temperature growth of nanostructures as a whole.

Rolled-up nanomembranes as compact 3D architectures for field effect transistors and fluidic sensing applications.

We fabricate inorganic thin film transistors with bending radii of less than 5 µm maintaining their high electronic performance with on-off ratios of more than 10(5) and subthreshold swings of 160 mV/dec. The fabrication technology relies on the roll-up of highly strained semiconducting nanomembranes, which compacts planar transistors into three-dimensional tubular architectures opening intriguing potential for microfluidic applications. Our technique probes the ultimate limit for the bending radius of high performance thin film transistors.

Waveguide-Coupled Light Photodetector Based on Two-Dimensional Molybdenum Disulfide.

The integration of transition metal dichalcogenides with photonic structures such as sol-gel SiOx:TiOy optical waveguides (WGs) makes possible the fabrication of photonic devices with the desired characteristics in the visible spectral range. In this study, we propose and experimentally demonstrate a MoS2-based photodetector integrated with a sol-gel SiOx:TiOy WG. Based on the spectroscopic measurements performed for our device, we concluded that the light entering the WG is almost completely channeled out from the WG and absorbed by the MoS2 flake, which is deposited on the WG. Therefore, this device works as a photodetector. The light coupling into the MoS2 region in this device construction is due to the high contrast of refractive index between the van der Waals crystal and the sol-gel WG, which is ∼4 and ∼1.8, respectively. The obtained MoS2-based photodetectors exhibit a photoresponsivity of 0.3 A W-1 (n-type MoS2) and 7.53 mA W-1 (p-type MoS2) at a bias voltage of 2 V. These results reveal great potential in the integration of sol-gel WGs with van der Waals crystals in optoelectronic applications.

Stability of mechanically exfoliated layered monochalcogenides under ambient conditions.

Monochalcogenides of groups III (GaS, GaSe) and VI (GeS, GeSe, SnS, and SnSe) are materials with interesting thickness-dependent characteristics, which have been applied in many areas. However, the stability of layered monochalcogenides (LMs) is a real problem in semiconductor devices that contain these materials. Therefore, it is an important issue that needs to be explored. This article presents a comprehensive study of the degradation mechanism in mechanically exfoliated monochalcogenides in ambient conditions using Raman and photoluminescence spectroscopy supported by structural methods. A higher stability (up to three weeks) was observed for GaS. The most reactive were Se-containing monochalcogenides. Surface protrusions appeared after the ambient exposure of GeSe was detected by scanning electron microscopy. In addition, the degradation of GeS and GeSe flakes was observed in the operando experiment in transmission electron microscopy. Additionally, the amorphization of the material progressed from the flake edges. The reported results and conclusions on the degradation of LMs are useful to understand surface oxidation, air stability, and to fabricate stable devices with monochalcogenides. The results indicate that LMs are more challenging for exfoliation and optical studies than transition metal dichalcogenides such as MoS2, MoSe2, WS2, or WSe2.

CVD-grown horizontally aligned single-walled carbon nanotubes: synthesis routes and growth mechanisms.

Single-walled carbon nanotubes (SWCNTs) have attractive electrical and physical properties, which make them very promising for use in various applications. For some applications however, in particular those involving electronics, SWCNTs need to be synthesized with a high degree of control with respect to yield, length, alignment, diameter, and chirality. With this in mind, a great deal of effort is being directed to the precision control of vertically and horizontally aligned nanotubes. In this review the focus is on the latter, horizontally aligned tubes grown by chemical vapor deposition (CVD). The reader is provided with an in-depth review of the established vapor deposition orientation techniques. Detailed discussions on the characterization routes, growth parameters, and growth mechanisms are also provided.

Sol-Gel Derived Silica-Titania Waveguide Films for Applications in Evanescent Wave Sensors-Comprehensive Study.

Composite silica-titania waveguide films of refractive index ca. 1.8 are fabricated on glass substrates using a sol-gel method and dip-coating technique. Tetraethyl orthosilicate and tetraethyl orthotitanate with molar ratio 1:1 are precursors. Fabricated waveguides are annealed at 500 °C for 60 min. Their optical properties are studied using ellipsometry and UV-Vis spectrophotometry. Optical losses are determined using the streak method. The material structure and chemical composition, of the silica-titania films are analyzed using transmission electron microscopy (TEM) and electron dispersive spectroscopy (EDS), respectively. The surface morphology was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM) methods. The results presented in this work show that the waveguide films are amorphous, and their parameters are stable for over a 13 years. The optical losses depend on their thickness and light polarization. Their lowest values are less than 0.06 dB cm-1. The paper presents the results of theoretical analysis of scattering losses on nanocrystals and pores in the bulk and interfaces of the waveguide film. These results combined with experimental data clearly indicate that light scattering at the interface to a glass substrate is the main source of optical losses. Presented waveguide films are suitable for application in evanescent wave sensors.