Graphene is a two-dimensional (2D) material with over 100-fold anisotropy of heat flow between the in-plane and out-of-plane directions. High in-plane thermal conductivity is due to covalent sp(2) bonding between carbon atoms, whereas out-of-plane heat flow is limited by weak van der Waals coupling. Herein, we review the thermal properties of graphene, including its specific heat and thermal conductivity (from diffusive to ballistic limits) and the influence of substrates, defects, and other atomic modifications. We also highlight practical applications in which the thermal properties of graphene play a role. For instance, graphene transistors and interconnects benefit from the high in-plane thermal conductivity, up to a certain channel length. However, weak thermal coupling with substrates implies that interfaces and contacts remain significant dissipation bottlenecks. Heat flow in graphene or graphene composites could also be tunable through a variety of means, including phonon scattering by substrates, edges, or interfaces. Ultimately, the unusual thermal properties of graphene stem from its 2D nature, forming a rich playground for new discoveries of heat-flow physics and potentially leading to novel thermal management applications.
Gas-turbine engines used in transportation, energy, and defense sectors rely on high-temperature thermal-barrier coatings (TBCs) for improved efficiencies and power. The promise of still higher efficiencies and other benefits is driving TBCs research and development worldwide. An introduction to TBCs-complex, multi-layer evolving systems-is presented, where these fascinating systems touch on several known phenomena in materials science and engineering. Critical elements identified as being important to the development of future TBCs form the basis for the five articles in this issue of MRS Bulletin. These articles are introduced, together with a discussion of the major challenges to improved coating development and the rich opportunities for materials research they provide.
Markets for energy storage that go beyond portable electronics have emerged rapidly this decade, including powering electric vehicles and "leveling the grid" fed by renewable sources such as solar energy, which are intermittent in supply. These new demands require a significant step-up in energy density that will probably not be met by Li-ion batteries; estimates suggest they are starting to approach their theoretical limits. But in the world of "beyond Li-ion," the options are limited. One of the most hopeful is the Li-S battery, for which greater energy storage can potentially be realized through phase-transformation chemistry using elemental sulfur as a positive electrode material, which converts to lithium sulfide. These future generation systems offer up to a five-fold increased specific energy and greatly reduced cost factors, but commercialization has been hindered owing to key challenges. Efforts over the last two years to better manipulate the cell chemistry and overcome these challenges are presented.
Metals possess the highest conductivity among all room-temperature materials; however, ultrathin metal films demonstrate decent optical transparency but poor sheet conductance due to electron scattering from the surface and grain boundaries. This article discusses engineered metal nanostructures in the form of nanogrids, nanowires, or continuous nanofibers as efficient transparent and conductive electrodes. Metal nanogrids are discussed, as they represent an excellent platform for understanding the fundamental science. Progress toward low-cost, nano-ink-based printed silver nanowire electrodes, including silver nanowire synthesis, film fabrication, wire-wire junction resistance, optoelectronic properties, and stability, are also discussed. Another important factor for low-cost application is to use earth-abundant materials. Copper-based nanowires and nanofibers are discussed in this context. Examples of device integrations of these materials are also given. Such metal nanostructure-based transparent electrodes are particularly attractive for solar cell applications.
Phase change memory (PCM) is an emerging technology that combines the unique properties of phase change materials with the potential for novel memory devices, which can help lead to new computer architectures. Phase change materials store information in their amorphous and crystalline phases, which can be reversibly switched by the application of an external voltage. This article describes the advantages and challenges of PCM. The physical properties of phase change materials that enable data storage are described, and our current knowledge of the phase change processes is summarized. Various designs of PCM devices with their respective advantages and integration challenges are presented. The scaling limits of PCM are addressed, and its performance is compared to competing existing and emerging memory technologies. Finally, potential new applications of phase change devices such as neuromorphic computing and phase change logic are outlined.
Using epitaxy and the misfit strain imposed by an underlying substrate, it is possible to elastically strain oxide thin films to percent levels-far beyond where they would crack in bulk. Under such strains, the properties of oxides can be dramatically altered. In this article, we review the use of elastic strain to enhance ferroics, materials containing domains that can be moved through the application of an electric field (ferroelectric), a magnetic field (ferromagnetic), or stress (ferroelastic). We describe examples of transmuting oxides that are neither ferroelectric nor ferromagnetic in their unstrained state into ferroelectrics, ferromagnets, or materials that are both at the same time (multiferroics). Elastic strain can also be used to enhance the properties of known ferroic oxides or to create new tunable microwave dielectrics with performance that rivals that of existing materials. Results show that for thin films of ferroic oxides, elastic strain is a viable alternative to the traditional method of chemical substitution to lower the energy of a desired ground state relative to that of competing ground states to create materials with superior properties.
Surface-enhanced Raman spectroscopy (SERS) is highly dependent upon the substrate, where excitation of the localized metal surface plasmon resonance enhances the vibrational scattering signal of proximate analyte molecules. This article reviews recent progress in the fabrication of SERS substrates and the requirements for characterization of plasmonic materials as SERS platforms. We discuss bottom-up fabrication of SERS substrates and illustrate the advantages of rational control of metallic nanoparticle synthesis and assembly for hot spot creation. We also detail top-down methods, including nanosphere lithography for the preparation of tunable, highly sensitive, and robust substrates, as well as the unique benefits of tip-enhanced Raman spectroscopy for simultaneous acquisition of molecular vibrational information and high spatial resolution imaging. Finally, we discuss future prospects and challenges in SERS, including the development of surface-enhanced femtosecond stimulated Raman spectroscopy, microfluidics with SERS, creating highly reproducible substrates, and the need for reliable characterization of substrates.
In a manner reminiscent of macroscale bending and folding techniques such as origami, the out-of-plane assembly of lithographically micro- and nanopatterned thin films, can be used to fabricate three-dimensional (3D) micro- and nanostructured devices. These 3D devices, including microelectronic circuits, sensors, antennas, metamaterials, robotic, and biomimetic constructs, enable new functionalities and are challenging to fabricate by other methods. In this article, we summarize important features of this set of techniques and the devices assembled thereof, with a focus on functional constructs that have been formed by bending, folding, or buckling. At small size scales, manipulation using manual or even wired probes face daunting practical challenges in terms of cost, scalability, and high-throughput manufacturability; hence we emphasize techniques that manipulate strain in thin films so that they can spontaneously assemble into programmed 3D geometries without the need for any wires or probes.
The high specific capacity, reactivity, and abundance of magnesium in the earth's crust and the relatively good safety features of Mg metal, despite its being a reactive metal, drive intensive efforts to develop rechargeable Mg batteries as a follow-up to the success of Li-ion battery technology. However, Mg anodes cannot function in usual non-aqueous electrolyte solutions. Consequently, it is important to develop unique, complex solutions for reversible Mg metal anodes. Also, finding relevant cathode materials that can reversibly insert bivalent Mg ions is a great challenge, In this article, we review the efforts and success in the development of several families of electrolyte solutions for secondary Mg batteries, in which Mg anodes behave fully reversibly, but also exhibit the necessary wide electrochemical window. We also review attempts to develop positive electrodes for rechargeable Mg batteries. The first generation of secondary Mg batteries has already been demonstrated, but their specific energy density remains relatively low. The challenge now is to develop novel Mg battery prototypes that possess high energy density.
Research in ABO(3) perovskite oxides ranges from fundamental scientific studies in superconductivity and magnetism to technologies for advanced low-power electronics, energy storage, and conversion. The breadth in functionalities observed in this versatile materials class originates, in part, from the ability to control the local and extended crystallographic structure of corner-connected octahedral units. While an established paradigm exists to alter the size, shape, and connectivity of the octahedral building blocks in bulk materials, these approaches are often limited to certain subsets of the allowed perovskite archetypes and chemistries. In this article, we describe emerging routes in thin films and multilayer superlattices enabled by epitaxial synthesis aimed at engineering the octahedral connectivity-rotational magnitudes and patterns-to reach unexplored portions of the crystallographic structure-property phase space for rational materials design. We review three promising chemistry-independent strategies that provide a handle to tune the octahedral connectivity: epitaxial strain, interfacial control at perovskite/perovskite heterojunctions, and rotation engineering in short-period superlattices. Finally, we touch upon potential new functionalities that could be attained by extending these approaches to static and dynamic manipulation of the perovskite structure through external fields and highlight unresolved questions for the deterministic control of octahedral rotations in perovskite-structured materials.
Electronics can be made on elastically stretchable "skin." Such skins conform to irregularly curved surfaces and carry arrays of thin-film devices and integrated circuits. Laypeople and scientists intuitively grasp the concept of electronic skins; material scientists then ask "what materials are used?" and "how does it work?" Stretchable circuits are made of diverse materials that span more than 12 orders of magnitude in elastic modulus. We begin with a brief overview of the materials and the architecture of stretchable electronics, then we discuss stretchable substrates, encapsulation, interconnects, and the fabrication of devices and circuits. These components and techniques provide the tools for creating new concepts in biocompatible circuits that conform to and stretch with living tissue. They enable wireless energy transfer via stretchable antennas, stretchable solar cells that convert sunlight to electricity, supercapacitors, and batteries that store energy in stretchable electronic devices. We conclude with a brief outlook on the technical challenges for this revolutionary technology on its road to functional stretchable electronic systems.
Condensation is a phase change phenomenon often encountered in nature, as well as used in industry for applications including power generation, thermal management, desalination, and environmental control. For the past eight decades, researchers have focused on creating surfaces allowing condensed droplets to be easily removed by gravity for enhanced heat transfer performance. Recent advancements in nanofabrication have enabled increased control of surface structuring for the development of superhydrophobic surfaces with even higher droplet mobility and, in some cases, coalescence-induced droplet jumping. Here, we provide a review of new insights gained to tailor superhydrophobic surfaces for enhanced condensation heat transfer considering the role of surface structure, nucleation density, droplet morphology, and droplet dynamics. Furthermore, we identify challenges and new opportunities to advance these surfaces for broad implementation in thermofluidic systems.
Molten deposits based on calcium-magnesium alumino-silicates (CMAS), originating from siliceous debris ingested with the intake air, represent a fundamental threat to progress in gas turbine technology by limiting the operating surface temperature of coated components. The thermomechanical and thermochemical aspects of the CMAS interactions with thermal-barrier coatings, as well as the current status of mitigating strategies, are discussed in this article. Key challenges and research needs for developing adequate solutions are highlighted.
Ongoing technological advances in such disparate areas as consumer electronics, transportation, and energy generation and distribution are often hindered by the capabilities of current energy storage/conversion systems, thereby driving the search for high-performance power sources that are also economically viable, safe to operate, and have limited environmental impact. Electrochemical capacitors (ECs) are a class of energy-storage devices that fill the gap between the high specific energy of batteries and the high specific power of conventional electrostatic capacitors. The most widely available commercial EC, based on a symmetric configuration of two high-surface-area carbon electrodes and a nonaqueous electrolyte, delivers specific energies of up to similar to 6 Whkg(-1) with sub-second response times. Specific energy can be enhanced by moving to asymmetric configurations and selecting electrode materials (e.g., transition metal oxides) that store charge via rapid and reversible faradaic reactions. Asymmetric EC designs also circumvent the main limitation of aqueous electrolytes by extending their operating voltage window beyond the thermodynamic 1.2 V limit to operating voltages approaching similar to 2 V, resulting in high-performance ECs that will satisfy the challenging power and energy demands of emerging technologies and in a more economically and environmentally friendly form than conventional symmetric ECs and batteries.
This issue contains assessments of battery performance involving complex, interrelated physical and chemical processes between electrode materials and electrolytes. Transformational changes in battery technologies are critically needed to enable the effective use of renewable energy sources such as solar and wind to allow for the expansion of hybrid electric vehicles (HEVs) to plug-in HEVs and pure-electric vehicles. For these applications, batteries must store more energy per unit volume and weight, and they must be capable of undergoing many thousands of charge-discharge cycles. The articles in this theme issue present details of several growing interest areas, including high-energy cathode and anode materials for rechargeable Li-ion batteries and challenges of Li metal as an anode material for Li batteries. They also address the recent progress in systems beyond Li ion, including Li-S and Li-air batteries, which represent possible next-generation batteries for electrical vehicles. One article reviews the recent understanding and new strategies and materials for rechargeable Mg batteries. The knowledge presented in these articles is anticipated to catalyze the design of new multifunctional materials that can be tailored to provide the optimal performance required for future electrical energy storage applications.
Piezoelectric microelectromechanical systems (MEMS) have been proven to be an attractive technology for harvesting small magnitudes of energy from ambient vibrations. This technology promises to eliminate the need for replacing chemical batteries or complex wiring in microsensors/microsystems, moving us closer toward battery-less autonomous sensors systems and networks. To achieve this goal, a fully assembled energy harvester the size of a US quarter dollar coin (diameter = 24.26 mm, thickness = 1.75 mm) should be able to robustly generate about 100 mu W of continuous power from ambient vibrations. In addition, the cost of the device should be sufficiently low for mass scale deployment. At the present time, most of the devices reported in the literature do not meet these requirements. This article reviews the current state of the art with respect to the key challenges such as high power density and wide bandwidth of operation. This article also describes improvements in piezoelectric materials and resonator structure design, which are believed to be the solutions to these challenges. Epitaxial growth and grain texturing of piezoelectric materials is being developed to achieve much higher energy conversion efficiency. For embedded medical systems, lead-free piezoelectric thin films are being developed, and MEMS processes for these new classes of materials are being investigated. Nonlinear resonating beams for wide bandwidth resonance are also being developed to enable more robust operation of energy harvesters.
Conventional silicon transistor scaling is fast approaching its limits. An extension of the logic device roadmap to further improve future performance increases of integrated circuits is required to propel the electronics industry. Attention is turning to III-V compound semiconductors that are well positioned to replace silicon as the base material in logic switching devices. Their outstanding electron transport properties and the possibility to tune heterostructures provide tremendous opportunities to engineer novel nanometer-scale logic transistors. The scaling constraints require an evolution from planar III-V metal oxide semiconductor field-effect transistors (MOSFETs) toward transistor channels with a three-dimensional structure, such as nanowire FETs, to achieve future performance needs for complementary metal oxide semiconductor (CMOS) nodes beyond 10 nm. Further device innovations are required to increase energy efficiency. This could be addressed by tunnel FETs (TFETs), which rely on interband tunneling and thus require advanced III-V heterostructures for optimized performance. This article describes the challenges and recent progress toward the development of III-V MOSFETs and heterostructure TFETs-from planar to nanowire devices-integrated on a silicon platform to make these technologies suitable for future CMOS applications.
Considering the need for designing better batteries to meet the rapidly growing demand for large-scale energy storage applications, an aspect of primary importance for battery materials is elemental abundance. To achieve sustainable energy development, we must reconsider the feasibility of a sustainable lithium supply, which is essential for lithium(-ion) batteries. Lithium is widely distributed in the Earth, but is not regarded as an abundant element. Therefore, widespread use of large-scale lithium batteries would be inevitably restricted. Sodium (-ion) batteries are thus promising candidates for large-scale applications because sodium is the most advantageous next to lithium considering its atomic weight, standard potential, and natural abundance. Rechargeable sodium-ion batteries consist of two different sodium insertion materials similar to Li-ion batteries. Sodium insertion materials, especially layered oxides, have been studied since the early 1980s, but not extensively for energy storage devices due to the expanded interest in lithium insertion materials in the 1990s. In recent years, materials researchers have again been extensively exploring new sodium insertion materials to enhance battery performance. This article reviews recent advancements and trends in layered sodium transition metal oxides as positive electrode materials for Na-ion batteries.
Elastic strain engineering offers a new route to enable high-performance catalysts, electrochemical energy conversion devices, separation membranes and memristors. By applying mechanical stress, the inherent energy landscape of reactions involved in the material can be altered. This is the so-called mechano-chemical coupling. Here we discuss how elastic strain activates reactions on metals and oxides. We also present analogies to strained polymer reactions. A rich set of investigations have been performed on strained metal surfaces over the last 15 years, and the mechanistic reasons behind strain-induced reactivity are explained by an electronic structure model. On the other hand, the potential of strain engineering of oxides for catalytic and energy applications has been largely underexplored. In oxides, mechanical stress couples to reaction and diffusion kinetics by altering the oxygen defect formation enthalpy, migration energy barrier, adsorption energy, dissociation barrier, and charge transfer barrier. A generalization of the principles for stress activated reactions from polymers to metals to oxides is offered, and the prospect of using elastic strain to tune reaction and diffusion kinetics in functional oxides is discussed.
Emerging telecommunication and data routing applications anticipate a photonic roadmap leading to ultra-compact photonic integrated circuits. Consequently, photonic devices will soon have to meet footprint and efficiency requirements similar to their electronic counterparts calling for extreme capabilities to create, guide, modulate, and detect deep-subwavelength optical fields. For active devices such as modulators, this means fulfilling optical switching operations within light propagation distances of just a few wavelengths. Plasmonics, or metal optics, has emerged as one potential solution for integrated on-chip circuits that can combine both high operational speeds and ultra-compact architectures rivaling electronics in both speed and critical feature sizes. This article describes the current status, challenges, and future directions of the various components required to realize plasmonic integrated circuitry.