As elemental main group materials (i.e., silicon and germanium) have dominated the field of modern electronics, their monolayer 2D analogues have shown great promise for next‐generation electronic ...materials as well as potential game‐changing properties for optoelectronics, energy, and beyond. These atomically thin materials composed of single atomic variants of group III through group VI elements on the periodic table have already demonstrated exciting properties such as near‐room‐temperature topological insulation in bismuthene, extremely high electron mobilities in phosphorene and silicone, and substantial Li‐ion storage capability in borophene. Isolation of these materials within the postgraphene era began with silicene in 2010 and quickly progressed to the experimental identification or theoretical prediction of 15 of the 18 main group elements existing as solids at standard pressure and temperatures. This review first focuses on the significance of defects/functionalization, discussion of different allotropes, and overarching structure–property relationships of 2D main group elemental materials. Then, a complete review of emerging applications in electronics, sensing, spintronics, plasmonics, photodetectors, ultrafast lasers, batteries, supercapacitors, and thermoelectrics is presented by application type, including detailed descriptions of how the material properties may be tailored toward each specific application.
Elemental 2D materials are some of the more exciting nanomaterials of interest due to their unique and tailorable properties. Recent progress in these exciting materials relative to their potential impact in applications including electronics, optoelectronics, and energy systems is presented.
Metal halide perovskites have emerged as exceptional semiconductors for optoelectronic applications. Substitution of the monovalent cations has advanced luminescence yields and device efficiencies. ...Here, we control the cation alloying to enhance optoelectronic performance through alteration of the charge carrier dynamics in mixed-halide perovskites. In contrast to single-halide perovskites, we find high luminescence yields for photoexcited carrier densities far below solar illumination conditions. Using time-resolved spectroscopy we show that the charge carrier recombination regime changes from second to first order within the first tens of nanoseconds after excitation. Supported by microscale mapping of the optical bandgap, electrically gated transport measurements and first-principles calculations, we demonstrate that spatially varying energetic disorder in the electronic states causes local charge accumulation, creating p- and n-type photodoped regions, which unearths a strategy for efficient light emission at low charge-injection in solar cells and light-emitting diodes.Localized photodoping in mixed-cation perovskites is shown to modify charge-carrier recombination and thus offer a route for more efficient light emission.
Surface enhanced Raman spectroscopy (SERS) is a powerful vibrational spectroscopy technique that allows for highly sensitive structural detection of low concentration analytes through the ...amplification of electromagnetic fields generated by the excitation of localized surface plasmons. SERS has progressed from studies of model systems on roughened electrodes to highly sophisticated studies, such as single molecule spectroscopy. We summarize the current state of knowledge concerning the mechanism of SERS and new substrate materials. We highlight recent applications of SERS including sensing, spectroelectrochemistry, single molecule SERS, and real-world applications. We also discuss contributions to the field from the Van Duyne group. This review concludes with a discussion of future directions for this field including biological probing with UV-SERS, tip-enhanced Raman spectroscopy, and ultrafast SERS.
The cathodic oxygen reduction reaction (ORR) is essential in the electrochemical energy conversion of fuel cells. Here, through the NH3 atmosphere annealing of a graphene oxide (GO) precursor ...containing trace amounts of Ru, we have synthesized atomically dispersed Ru on nitrogen-doped graphene that performs as an electrocatalyst for the ORR in acidic medium. The Ru/nitrogen-doped GO catalyst exhibits excellent four-electron ORR activity, offering onset and half-wave potentials of 0.89 and 0.75 V, respectively, vs a reversible hydrogen electrode (RHE) in 0.1 M HClO4, together with better durability and tolerance toward methanol and carbon monoxide poisoning than seen in commercial Pt/C catalysts. X-ray adsorption fine structure analysis and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy are performed and indicate that the chemical structure of Ru is predominantly composed of isolated Ru atoms coordinated with nitrogen atoms on the graphene substrate. Furthermore, a density function theory study of the ORR mechanism suggests that a Ru-oxo-N4 structure appears to be responsible for the ORR catalytic activity in the acidic medium. These findings provide a route for the design of efficient ORR single-atom catalysts.
Recently, two-dimensional layers of transition metal dichalcogenides, such as MoS2, WS2, MoSe2, and WSe2, have attracted much attention for their potential applications in electronic and ...optoelectronic devices. The selenide analogues of MoS2 and WS2 have smaller band gaps and higher electron mobilities, making them more appropriate for practical devices. However, reports on scalable growth of high quality transition metal diselenide layers and studies of their properties have been limited. Here, we demonstrate the chemical vapor deposition (CVD) growth of uniform MoSe2 monolayers under ambient pressure, resulting in large single crystalline islands. The photoluminescence intensity and peak position indicates a direct band gap of 1.5 eV for the MoSe2 monolayers. A back-gated field effect transistor based on MoSe2 monolayer shows n-type channel behavior with average mobility of 50 cm2 V–1 s–1, a value much higher than the 4–20 cm2 V–1 s–1 reported for vapor phase grown MoS2.
Localized surface plasmon resonances have attracted much attention due to their ability to enhance light–matter interactions and manipulate light at the subwavelength level. Recently, alternatives to ...the rare and expensive noble metals Ag and Au have been sought for more sustainable and large-scale plasmonic utilization. Mg supports plasmon resonances, is one of the most abundant elements in earth’s crust, and is fully biocompatible, making it an attractive framework for plasmonics. This feature article first reports the hexagonal, folded, and kite-like shapes expected theoretically from a modified Wulff construction for single crystal and twinned Mg structures and describes their excellent match with experimental results. Then, the optical response of Mg nanoparticles is overviewed, highlighting Mg’s ability to sustain localized surface plasmon resonances across the ultraviolet, visible, and near-infrared electromagnetic ranges. The various resonant modes of hexagons, leading to the highly localized electric field characteristic of plasmonic behavior, are presented numerically and experimentally. The evolution of these modes and the associated field from hexagons to the lower symmetry folded structures is then probed, again by matching simulations, optical, and electron spectroscopy data. Lastly, results demonstrating the opportunities and challenges related to the high chemical reactivity of Mg are discussed, including surface oxide formation and galvanic replacement as a synthetic tool for bimetallics. This Feature Article concludes with a summary of the next steps, open questions, and future directions in the field of Mg nanoplasmonics.
The isolation of graphene in 2004 from graphite was a defining moment for the “birth” of a field: two-dimensional (2D) materials. In recent years, there has been a rapidly increasing number of papers ...focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement. Here, we review significant recent advances and important new developments in 2D materials “beyond graphene”. We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies. Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (i.e., silicene, phosphorene, etc.) and transition metal carbide- and carbon nitride-based MXenes. We then discuss the doping and functionalization of 2D materials beyond graphene that enable device applications, followed by advances in electronic, optoelectronic, and magnetic devices and theory. Finally, we provide perspectives on the future of 2D materials beyond graphene.
Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, ...heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna–reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.
Most properties of nanocrystalline materials are shape-dependent, providing their exquisite tunability in optical, mechanical, electronic and catalytic properties. An example of the former is ...localized surface plasmon resonance (LSPR), the coherent oscillation of conduction electrons in metals that can be excited by the electric field of light; this resonance frequency is highly dependent on both the size and shape of a nanocrystal. An example of the latter is the marked difference in catalytic activity observed for different Pd nanoparticles. Such examples highlight the importance of particle shape in nanocrystalline materials and their practical applications. However, one may ask 'how are nanoshapes created?', 'how does the shape relate to the atomic packing and crystallography of the material?', 'how can we control and characterize the external shape and crystal structure of such small nanocrystals?'. This feature article aims to give the reader an overview of important techniques, concepts and recent advances related to these questions. Nucleation, growth and how seed crystallography influences the final synthesis product are discussed, followed by shape prediction models based on seed crystallography and thermodynamic or kinetic parameters. The crystallographic implications of epitaxy and orientation in multilayered, core-shell nanoparticles are overviewed, and, finally, the development and implications of novel, spatially resolved analysis tools are discussed.
Unlike in the bulk, at the nanoscale shape dictates properties. The imperative to understand and predict nanocrystal shape led to the development, over several decades, of a large number of ...mathematical models and, later, their software implementations. In this review, the various mathematical approaches used to model crystal shapes are first overviewed, from the century-old Wulff construction to the year-old (2020) approach to describe supported twinned nanocrystals, together with a discussion and disambiguation of the terminology. Then, the multitude of published software implementations of these Wulff-based shape models are described in detail, describing their technical aspects, advantages and limitations. Finally, a discussion of the scientific applications of shape models to either predict shape or use shape to deduce thermodynamic and/or kinetic parameters is offered, followed by a conclusion. This review provides a guide for scientists looking to model crystal shape in a field where ever-increasingly complex crystal shapes and compositions are required to fulfil the exciting promises of nanotechnology.
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