Layered transition metal oxides are some of the most important materials for high energy and power density electrochemical energy storage, such as batteries and electrochemical capacitors. These oxides can efficiently store charge via intercalation of ions into the interlayer vacant sites of the bulk material. The interlayer can be tuned to modify the electrochemical environment of the intercalating species to allow improved interfacial charge transfer and/or solid-state diffusion. The ability to fine-tune the solid-state environment for energy storage is highly beneficial for the design of layered oxides for specific mechanisms, including multivalent ion intercalation. This review focuses on the benefits as well as the methods for interlayer modification of layered oxides, which include the presence of structural water, solvent cointercalation and exchange, cation exchange, polymers, and small molecules, exfoliation, and exfoliated heterostructures. These methods are an important design tool for further development of layered oxides for electrochemical energy storage applications.

The lithium ion battery is the most promising battery candidate to power battery electric vehicles. For these vehicles to be competitive with those powered by conventional internal combustion engines, significant improvements in battery performance are needed, especially in the energy density and power delivery capabilities. Promising substitutes for graphite as the anode material include silicon, tin, germanium, and various metal oxides that have much higher theoretical storage capacities and operated at slightly higher and safer potentials. In this critical review, metal oxides-based materials for lithium ion battery anodes are reviewed in detail together with the progress which is made in my lab on that topic. Their advantages, disadvantages, and performance in lithium ion batteries are discussed through extensive analysis of the literature, and new trends in materials development are also reviewed. Two important future research directions are proposed and performed in my lab, based on results published in the literature: the development of composite and nanostructured metal oxides to overcome the major challenge posed by the high capacity of metal oxide anodes.

Atomic layer deposition (ALD) of vanadium oxide (VOx ) thin films, using tetrakis(dimethylamino)vanadium as the vanadium precursor, is comprehensively reported in this work. The vanadium precursor is highly volatile and can be used at room temperature for deposition. Either H2O or O3 can be used as the coreactant for depositing VOx at 50–200 °C. However, partial precursor decomposition is suggested for the deposition temperature higher than 160 °C. The as-deposited VOx films are pure, smooth, and amorphous, and can be crystallized into monoclinic VO2 phase by postdeposition annealing under N2 ambient. The minimum annealing temperature for film to crystallize is found, by in situ high-temperature X-ray diffraction experiments, at around 550–600 °C. In situ quartz crystal microbalance experiments are performed to further analyze the surface reaction mechanism involved in this ALD process.

Perovskite-based solar cells, typically CH3NH3PbI3, have reached power conversion efficiencies on par with single crystal silicon solar cells. Perovskite cells prepared with the most common perovskite solvent N,N-dimethylformamide (DMF) by different research groups exhibit disparate efficiencies and stability for nominally identical perovskite films. Although the differences can be related to processing conditions, a consistent physical cause for the differences has been lacking. Highly-sensitive time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveals significant dimethylamine (DMA) included in perovskite films. TOF-SIMS and x-ray photoelectron spectroscopy results suggest DMA levels ranging from roughly 10–50%. Only the highest levels register as perovskite peak shifts in x-ray diffraction; lower levels are invisible. We propose that methylamine (MA) can react with DMF solvent by transamidation to produce dimethylamine (DMA), which then displaces some MA in perovskite crystals, see Fig. 1. Transamidation of DMF can be catalyzed by TiO2, Al2O3, water, or acid, but in perovskite films transamidation is inhibited by water.

Materials for scintillator radiation detectors need to fulfill a diverse set of requirements such as radiation hardness and highly specific response to incoming radiation, rendering them a target of current materials design efforts. Even though they are amenable to cutting-edge theoretical spectroscopy techniques, surprisingly many fundamental properties of scintillator materials are still unknown or not well explored. In this work, we use first-principles approaches to thoroughly study the optical properties of four scintillator materials: NaI, LaBr3, BaI2, and SrI2. By solving the Bethe–Salpeter equation for the optical polarization function we study the influence of excitonic effects on dielectric and electron-energy loss functions. This work sheds light into fundamental optical properties of these four scintillator materials and lays the ground-work for future work that is geared toward accurate modeling and computational materials design of advanced radiation detectors with unprecedented energy resolution.

Recently, various two-dimensional (2D) materials, such as graphene, transition metal dichalcogenides and so on, have attracted much attention in electron device research. The most important characteristic of graphene is its highest mobility of all semiconductor channels at room temperature. However, it is obvious that more than a good mobility characteristic is required to realize the field effect transistor (FET), and intense arguments from various points of view are necessary. In this paper, the issues with Si-metal oxide semiconductor FETs (Si-MOSFET) and the advantage of 2D materials are discussed. The present state of graphene FETs with respect to gate stack formation and band gap engineering is reported. Moreover, based on the density of states (DOS) of graphene extracted using the quantum capacitance (C Q) measurement, it is shown that the electric band structure of graphene in contact with gate insulators or metal electrode deviates from its intrinsic band structure.

Polyaniline (PANI)/11% Multi-carbon nanotubes (MWCNT) nanocomposites sensors were synthesized through an in situ polymerization method. Frits compression method was adopted to make PANI/MWCNT. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) tests results showed that this technique produced a coating of PANI onto the MWCNT, which indicated that CNT were well dispersed in the polymer matrix. Several tests were run to evaluate the sensor's capabilities. The free end vibration test results showed that the double sided attachment of the sensor had higher damping ratio values than single sided attachment. Also, damping ratios were higher when the sensor was placed at the clamped end. Further, the strain sensing properties of PANI/MWCNT sensors were compared with the conventional foil strain gage. The dynamic sensing test results showed that over the range of 10–1000 Hz, the PANI/MWCNT composite sensor was consistently superior to the traditional foil strain gage for sensing purposes.

Research on graphene has been developing at a relentless pace as it holds the promise of delivering composites with exceptional properties. In particular, the excellent mechanical properties of graphene make it a potentially good reinforcement ingredient in ceramic composites while their impressive electrical conductivity has roused interest in the area of multifunctional applications. However, the potential of graphene can only be fully exploited if they are homogenously embedded into ceramic matrices. Thus, suitable processing route is critical in obtaining ceramic composites with desired properties. This paper reviews the current understanding of graphene ceramic matrix composites (GCMC) with three particular topics: (i) principles and techniques for graphene dispersion, (ii) processing of GCMC, and (iii) effects of graphene on properties of GCMC. Besides, toughening mechanisms and percolation phenomenon that may occur in these composites are elaborated with appropriate examples. Challenges and perspectives for future progress in applications are also highlighted.

Carbon-based nanomaterials (CANOMATs), including fullerenes, carbon nanotubes, graphene, and their derivatives, are widely considered to be the next-generation materials for a broad range of biomedical applications, owing to their unique opto-electronic, chemical, and mechanical properties. However, for bio-applications, CANOMATs need to be surface-functionalized, to render them passive, non-toxic, and water-soluble. Here, we review the current state-of-the-art in the methods of functionalization of CANOMATs. In contrast to other Reviews, we present an objective analysis of the various approaches reported in the literature, using metrics such as the agent of functionalization, number of steps, and time required, the need for special instruments, effect on properties, scalability, reproducibility, and applications. Our Review offers a way for researchers to make a rational selection of the process of functionalization to best suit their desired application. This opens up new opportunities for developing targeted functionalization strategies, based on the need to excel at the above metrics.

Controlling the spatial arrangement of biomaterials and living cells provides the foundation for fabricating complex biological systems. Such level of spatial resolution (less than 10 µm) is difficult to be obtained through conventional cell processing techniques, which lack the precision, reproducibility, automation, and speed required for the rapid fabrication of engineered tissue constructs. Recently, laser-assisted biofabrication techniques are being intensively developed with the use of computer-aided processes for patterning and assembling both living and nonliving materials with prescribed 2D or 3D organization. In this review, we discuss laser-assisted fabrication methods, including laser tweezers, multi-photon polymerization, laser-induced forward transfer (LIFT), matrix assisted pulsed laser evaporation (MAPLE), and laser ablation as well as their applications in biological science and biomedical engineering. These advanced technologies enable the precise manipulation of in vitro cellular microenvironments and the ability to engineer functional tissue constructs with high complexity and heterogeneity, which serve in regenerative medicine, pharmacology, and basic cell biology studies.

Self-assembly of biocompatible nanoparticles is part of a promising field in drug delivery and biomaterials. Virus capsids are an example of nanoparticles capable of being tethered with functional groups for specific targeting. There have been experimental efforts on grafting polymers to virus capsids to synthesize tailored nanostructures. To provide insight at the nanoscale, we perform a highly coarse-grained molecular dynamics study, simulating the self-aggregation of cowpea mosaic virus (CPMV) capsids decorated with polyethylene glycol (PEG) and PEG polylactic acid (PLA) block polymers. We examined the effects of grafting architecture and volume fraction on equilibrated clusters. Characterization of the aggregation dynamics are summarized by the radius of gyration of the clusters, coordination number distributions, and average cluster size. When the system and methods are parameterized with respect to atomistic models or empirical results, the results can serve as the basis in broadly mapping the theoretical design space for controlled self-assembly of polymer-decorated virus capsids.

Aligned carbon nanotubes (CNTs) possess great potential for transforming the fabrication of advanced interfacial materials for energy and mass transport as well as for structural composites. Realizing this potential, however, requires building a deeper understanding and exercising greater control on the atomic scale physicochemical processes underlying the bottom-up synthesis and self-organization of CNTs. Hence, in situ nanoscale metrology and characterization techniques were developed for interrogating CNTs as they grow, interact, and self-assemble. This article presents an overview of recent research on characterization of CNT growth by chemical vapor deposition (CVD), organized into three categories based on the growth stage, for which each technique provides information: (I) catalyst preparation and treatment, (II) catalytic activation and CNT nucleation, and (III) CNT growth and termination. Combining all three categories together provides insights into building the process–structure relationship, and paves the way for producing tailored CNT structures having desired properties for target applications.

Nanocrystalline bulk materials (also called nanograined materials) are intrinsically unstable due to the excess grain boundary (GB) free energies. Dopants designed to segregate to boundaries have been proposed to lower excess GB energies, increasing stability against coarsening and enabling nanostructure features to survive high temperature processing and operational environments. It has been theoretically proposed that the GB energy of a material can eventually become zero as a function of dopant concentration, signifying negligible driving force for growth—an infinitely stable nanomaterial. In this work we use ultrasensitive microcalorimetry to experimentally measure the absolute GB energy of gadolinium-doped nanocrystalline zirconia as a function of grain size and show that the energy can indeed reach a quasi-zero energy state (∼0.05 J/m2) when a critical GB dopant enrichment is achieved. This thermodynamic condition leads to unprecedented coarsening resistance, but is a temperature dependent function; since increasing temperatures deplete the GB as the dopant dissolves back in the crystalline bulk.

By using a combination of experiments and molecular dynamics simulations, our studies show that the elastic response of silica glass to initial compression gradually changes from abnormal to normal with increasing quench pressure, helium content or alkali modifier added in the glass matrix. We uncovered the structural origin of the elastic anomaly in silica glass as localized structural transitions between motifs of different stiffness that are similar to those found in its crystalline counterparts. Pressure-quenching, helium-stuffing, or alkali-modifying plays a different role in changing the structure of silica glass, but all of the resulting structures reduce the propensity for such local structural transitions to take place, thus the degree of elastic anomaly. Our studies demonstrate that by processing in ways that gradually eliminates the elastic anomaly, the degree of silica glass to undergo irreversible densification can be eventually eradicated. This provides a solid foundation for the bottom-up design of new glasses with tunable structure and properties.

Over the years, the search for high performance thermoelectric materials has been dictated by the “phonon glass and electron crystal (PGEC)” paradigm, which suggests that low band gap semiconductors with high atomic number elements and high carrier mobility are the ideal materials to achieve high thermoelectric figure of merit. Complex oxides provide alternative mechanisms such as large density of states and strong electron correlation for high thermoelectric efficiency, albeit having low carrier mobility. Due to vast structural and chemical flexibility, they provide a fertile playground to design high efficiency thermoelectric materials. Further, developments in oxide thin film growth methods have enabled synthesis of high quality, atomically precise low dimensional structures such as heterostructures and superlattices. These materials and structures act as excellent model systems to explore nanoscale thermal and thermoelectric transport, which will not only expand the frontier of our knowledge, but also continue to enable cutting edge applications.

Thermal transport in materials used for energy applications is a physical process directly tied to performance and reliability. As a result, a great deal of effort has been devoted to understanding thermal transport in materials whose ability to conduct heat is critical. Here, our objective is to discuss the utility of laser-based thermoreflectance (TR) approaches that provide microscale measurement of thermal transport. We provide several examples that implement the TR technique to investigate thermal transport in materials used in nuclear energy applications. First, we discuss utility of this technique to measure thermal conductivity in ion irradiated ceramic materials during investigations where the primary objective is to understand the impact of radiation induced crystalline structure defects on thermal transport. We also present the capability of TR approach to resolve thermal conductivity of each layer in tristructural isotropic fuel, silicon carbide fiber composites, and 2nd phase precipitates in uranium silicide. Finally, the ability to measure interface thermal resistance between adjacent layers in composites is demonstrated.

Our study proposes in situ synthesis of cold-rollable aluminum nitride (AlN) reinforced aluminum matrix composites with attractive thermal properties via arc plasma-induced accelerated volume nitridation (APAVN). Within three minutes of repeated APAVN using commercial nitrogen gas, volume fraction of AlN increased up to 40 vol%, which is the highest value ever reported by in situ nitridation of pure aluminum. The composites contained homogeneously dispersed AlN particulates with strong interfacial bonding and low interfacial thermal resistance, which resulted in unique combination of a relatively low coefficient of thermal expansion and high specific thermal conductivity. APAVN resulted from instantaneous chemisorption of dissociated nitrogen, enhanced diffusion of dissolved nitrogen, and improved wettability, which led to much more AlN formation, ∼2.94 × 10−1 g/(min cm3), which is about 400 times higher than that in the gas bubbling method. These results would ultimately give us a promising strategy for continuous production of in situ Al–AlN composites for heat sink applications through cost-effective processing.

A consistent description of the hydrogen permeation through metal membrane based on hydrogen chemical potential proposed has been explained in detail. The hydrogen flux is proportional to the PCT factor, f PCT, consistently, which reflects the shape of the pressure-composition-isotherm (PCT curve) of the material. In addition, in view of the PCT factor, f PCT, and the ductile-to-brittle transition hydrogen concentration, DBTC, a concept for alloy design with high hydrogen permeability and strong resistance to hydrogen embrittlement has been proposed. In this concept, it is important to design alloy composition with appropriate PCT curve under the given pressure and temperature condition. As an example, V–9 mol% Al alloy has been designed, which exhibits high hydrogen flux without brittle fracture under given condition. Thus, the new consistent description is useful not only for the understanding of the hydrogen permeation property but also for the alloy design.

The manner in which structure at the mesoscale affects emergent collective dynamics has become the focus of much attention owing, in part, to new insights into how morphology on these spatial scales can be exploited for enhancement and optimization of macroscopic properties. Key to advancements in this area is development of multimodal characterization tools, wherein access to a large parameter space (energy, space, and time) is achieved (ideally) with a single instrument. Here, we describe the study of optomechanical responses of single-crystal Si cantilevers with an ultrafast electron microscope. By conducting structural-dynamics studies in both real and reciprocal space, we are able to visualize MHz vibrational responses from atomic- to micrometer-scale dimensions. With nanosecond selected-area and convergent-beam diffraction, we demonstrate the effects of spatial signal averaging on the isolation and identification of eigenmodes of the cantilever. We find that the reciprocal-space methods reveal eigenmodes mainly below 5 MHz, indicative of the first five vibrational eigenvalues for the cantilever geometry studied here. With nanosecond real-space imaging, however, we are able to visualize local vibrational frequencies exceeding 30 MHz. The heterogeneously-distributed vibrational response is mapped via generation of pixel-by-pixel time-dependent Fourier spectra, which reveal the localized high-frequency modes, whose presence is not detected with parallel-beam diffraction. By correlating the transient response of the three modalities, the oscillation, and dissipation of the optomechanical response can be compared to a linear-elastic model to isolate and identify the spatial three-dimensional dynamics.