Lead-free perovskite layers may provide a good alternative to the commonly used lead-halide-based perovskite absorber layers in photovoltaics. Energy level alignment of the active semiconductor with contact layers is a key factor in device performance. Kelvin probe force microscopy was used during vapor deposition of C60 onto formamidinium tin iodide to investigate contact formation with detailed local resolution of these materials that are significant for photovoltaic cells. Significant differences dependent on the growth rate of C60 were detected. Sufficiently high deposition rates were essential to reach compact C60 films needed for good contact. A space charge layer larger than 90 nm within the C60 layer was established without indication of interfacial dipoles. The present analysis gives a clear indication of a well-functioning contact of fullerenes to formamidinium tin iodide that is suitable for the use in photovoltaic devices provided that thin compact fullerene films are formed.

In this article, Si nanoparticle (NP) films were prepared by pulsed laser ablation (PLA) in the argon atmosphere of 10 Pa at room temperature under different pulse repetition rates from 1 to 40 Hz without the baffle. Different from the conventional PLA method, the substrates were placed below and parallel to the ablated plume axis. The obtained films containing NPs were characterized by scanning electron microscopy and Raman spectrometer. The experimental results under constant laser fluence demonstrate the strong dependence of the mean size and the area number density of NPs on the repetition rate. Specifically, with the increase of pulse repetition rate, the mean size of the NPs in the film first decreases and reaches its minimum at 20 Hz, and then increases after 20 Hz, and decreases again till 40 Hz. The area number density shows the contrary trend versus mean size. The in situ diagnostic results of Langmuir probe denote the ablated Si ion density increases monotonously with the increase of repetition rate, while the temperature is almost constant. Combining with the nucleation probability, the growth/aggregation duration of NPs in the “nucleation region” and the effect of the baffle, the influence of pulse repetition rate on the formation of NPs is addressed. It is found that the repetition rate impacts the growth modes of NPs (i.e., growth and aggregation). 1–20, 20–30, and 30–40 Hz, respectively, correspond to growth-, aggregation-, and growth-controlled rate ranges without the baffle; however, 1–10, 10–20, and 20–40 Hz, respectively, correspond to growth-controlled, aggregation/growth-coexisted, and aggregation-controlled rate ranges with the baffle.

Driven by the rapid rise of silicon photonics, optical signaling is moving from the realm of long-distance communications to chip-to-chip, and even on-chip domains. If on-chip signaling becomes optical, we should consider what more we might do with light than just communicate. We might, for example, set goals for the storing and processing of information directly in the optical domain. Doing this might enable us to supplement, or even surpass, the performance of electronic processors, by exploiting the ultrahigh bandwidth and wavelength division multiplexing capabilities offered by optics. In this article, we show how, by using an integrated photonics platform that embeds chalcogenide phase-change materials into standard silicon photonics circuits, we can achieve some of these goals. Specifically, we show that a phase-change integrated photonics platform can deliver binary and multilevel memory, arithmetic and logic processing, as well as synaptic and neuronal mimics for use in neuromorphic, or brain-like, computing—all working directly in the optical domain.

Nano-forms of copper oxides (CuO and Cu2O) are potential candidates in the field of energy conversion and storage. Low temperature and controlled growth of three-dimensional nanostructured hierarchical assembly of CuO over Cu2O is reported here with demonstrated advantage in energy conversion and storage applications. Electrodeposited Cu2O is partially oxidized in an alkali bath to two different forms of hierarchical nanostructures (HNS): CuO/Cu2O and CuO:Cu(OH)2/Cu2O. Randomly oriented nanorods and nanoflakes with high surface area tussock-like nanostructure are formed during oxidation at room and at elevated temperatures, respectively. The nanoflake morphology exhibits a high surface area of 85.82 m2/g and sufficient ion percolation pathways, leading to an efficient electrode–electrolyte interface for electrochemical energy devices. A favorable conduction and valence band alignment in the HNS with respect to water redox level along with fast electron diffusion time of 0.8 μs make it an ideal photocathode.

The kinetics of silica polymerization was measured in silicic acid solutions containing a suite of 0.1 M amino acids, 0.1 M citric acid, 0.7 M NaCl, and 0.10 M NaCl (Control). Fitting a modified classical rate model to measurements of induction time (τ) at 20 °C for a series of supersaturated solutions, we estimate the thermodynamic barrier (ΔGc), interfacial free energy (γ), and kinetic barrier (Δagk) for silica nucleation. For 0.10 M NaCl solutions, γControl = 54.9 ± 1.6 mJ/m2 and ΔagkControl = 2.29 × 10−19 J/mol. These values are consistent with previous reports for amorphous and fused silica materials. To facilitate comparisons with the treatments, ΔagkControl is converted to a molar basis and used as a reference datum, such that ΔagkControl = 0.0 J/mol. The effects of salt and organic acids on nucleation rate have thermodynamic and kinetic origins, respectively. Faster nucleation rates measured in 0.7 M NaCl solutions arise from a lower interfacial free energy, such that γ0.7 M NaCl = 51.4 ± 1.7 mJ/m2. Organic acids increase rate through biomolecule-specific reductions in Δagk. Catalytic effects are greatest for lysine (Δagklysine = −1685 ± 315) and citric acid (Δagkcitric = −1690 ± 96 J/mol). Reductions in the kinetic barrier correlate with net positive charge of the amino acids and dissociation of the amine $\left( {{K_{\alpha {\rm{ ‐ N}}{{\rm{H}}_3}^ {\bf{+}} }}} \right)$ group and thus the abundance of the conjugate base. Citric acid, lacking amine groups, promotes the greatest rate enhancement, thus demonstrating the role(s) of additional kinetic factors in promoting nucleation rate. Catalytic activity correlates with multiple physical and chemical properties of the organic acids.

Nature’s optical nanomaterials are poised to form the platform for future optical devices with unprecedented functionality. The brilliant colors of many animals arise from the physical interaction of light with nanostructured, multifunctional materials. While their length scale is typically in the 100-nm range, the morphology of these structures can vary strongly. These biological nanostructures are obtained in a controlled manner, using biomaterials under ambient conditions. The formation processes nature employs use elements of both equilibrium self-assembly and far-from-equilibrium and growth processes. This renders not only the colors themselves, but also the formation processes technologically and ecologically highly relevant. Yet, for many biological nanostructured materials, little is known about the formation mechanisms—partially due to a lack of in vivo imaging methods. Here, we present the toolbox of natural multifunctional nanostructures and the current knowledge about the understanding of their far-from-equilibrium assembly processes.

The crack initiation and early growth behaviors of a TC4 titanium alloy under high cycle fatigue and very high cycle fatigue were experimentally investigated. The results show that it exhibits the duplex S–N curve characteristics associated with surface and interior failures at a stress ratio of 0.1, while it represents the similar S–N curve characteristics only related to surface failure at a stress ratio of −1. The interior failure is accompanied with the occurrence of facets, granular bright facets (GBFs), and fisheye. Slip-like patterns are observable on the facets easily formed under positive stress ratio. The interior failure process is characterized as (i) occurrence of slip lines on partial α grains under cyclic loading, (ii) initiation and growth of microcracks within some α grains, (iii) coalescence of microcracks and formation of GBF, (iv) stable long crack growth within fisheye, (v) unstable crack growth outside fisheye, and (vi) final momentary fracture.

When the size and spacing of catalyst nanoparticles are well controlled on a substrate, carbon nanotubes (CNTs) can grow and assemble into a unique, vertically aligned structure frequently called a “forest.” Long, aligned, and pure CNTs can easily be synthesized in simple or highly complex configurations. First reported in 1996, CNT forests have been shown to be unique and useful forms of CNTs, as they have spurred the development of novel processes and applications and in addition, served as test beds for investigations into CNT growth mechanisms. This article provides an overview of two decades of research in this area.

Nanocarbons have been catalytically grown since 1993. However, even today, the formation mechanisms of carbon nanotubes (CNTs) and graphene are not sufficiently understood. This sustained challenge has been an engine for the development in theory concepts and computational methods, tackling the problem of well-controlled production of these nanomaterials. This article discusses how experimental discoveries and theoretical approaches evolved hand-in-hand for the successful understanding of challenging issues, highlighting parallels and distinctions between graphene and CNTs. Key aspects include the mechanisms of nucleation and CNT-liftoff, chiral symmetry selection and control, rates of growth and island shapes, mechanisms defining single chirality of the nanotubes, and ways to suppress grain boundaries in the quest for ever larger and faster growing single-crystal graphene, or longest defect-free CNTs. The theme of catalyst chemistry and structure, either as a nanoparticle or a planar substrate, is traced through the stages of nanocarbon formation, with focus on theoretically generalizable findings.

Nucleation is the seminal process in the formation of ordered structures ranging from simple inorganic crystals to macromolecular matrices. Observations over the past 15 years have revealed a rich set of hierarchical nucleation pathways involving higher-order species ranging from multi-ion clusters to dense liquid droplets, as well as transient crystalline or amorphous phases. Despite this complexity, the pathways that lead to nucleation can be described by a holistic framework that is rooted in classical concepts, but which takes into account the coupled effects of perturbations in free-energy landscapes and the impact of dynamical factors. This article describes that framework using a series of in situ transmission electron microscopy and atomic force microscopy studies on inorganic, organic, and macromolecular systems to illustrate the evolution in nucleation processes as these perturbations and dynamical factors come into play. The results provide a common basis for understanding development of order in systems as diverse as simple salt crystals, branched semiconductor nanowires, and microbial membranes.

Materials designed and engineered for technical applications must invariably meet or exceed multiple key specifications. Even if commercial realization is not intended, scientific interest is piqued if a challenging combination of properties is achieved, particularly if they are mutually exclusive for certain classes of materials. For example, the combination of mechanical toughness, chemical durability, and high thermal-shock resistance, with pore-free, smooth, aesthetically beautiful surfaces simultaneously realized in certain glasses that are crystallized in a controlled manner—glass-ceramics—have enabled two distinct, decades-long applications, cookware and flat cooktop panels. Other special glass-ceramic materials have been developed for electronic, photonic, dental, and biomedical applications. No other class of material could combine these properties in such an advantageous and economically feasible manner. This issue highlights six very different innovative applications of glass-ceramics, all of which owe their importance and continuing interest to “hard-to-combine” properties.

Crystallization in glasses is usually considered to be a problem in the glass industry. However, controlled crystallization of glasses is an important prerequisite in the development of glass-ceramics with tailored useful properties. Similar boundary conditions apply when considering glass-ceramics for the immobilization of nuclear waste via vitrification. While uncontrolled crystallization in nuclear-waste glasses is problematic, chemically durable glass-ceramics with significantly high waste loadings can be produced with controlled crystallization of glasses. This article presents an overview of various aspects of nuclear-waste glasses where crystallization is either considered to be advantageous or problematic. The classification of glass-ceramic waste forms and strategies to design glass-ceramics for a given waste stream is discussed. Some open and relevant problems faced by researchers developing nuclear-waste glass-ceramics are also offered.

In the present study, nano-sized cuboid-shaped particles in Mg–Nd–Y are studied by means of Cs-corrected atomic-scale high-angle annular dark-field scanning transmission electron microscopy. The structure of the cuboid-shaped phase is identified to be yttrium (major component) and neodymium atoms in face-centered cubic arrangement without the participation of Mg. The lattice parameter a=5.15 Å. During isothermal aging at 225°C, Mg3(Nd,Y) precipitates adhere to surface (100) planes of the cuboid-shaped particles with the orientation relationship: $[100]_{{{\rm Mg}_{{\rm 3}} {\rm RE}}} \,/\,\,/\,[100]_{{{\rm Cuboid}}} $ and $[310]_{{{\rm Mg}_{{\rm 3}} {\rm RE}}} \,/\,\,/\,[012]_{{{\rm Cuboid}}} $ . The fully coherent interfaces between the precipitates and the cuboid-shaped phases are reconstructed and categorized into two types: $(400)_{{{\rm Mg}_{{\rm 3}} {\rm RE}}} $ interface and $(200)_{{{\rm Mg}_{{\rm 3}} {\rm RE}}} $ interface.

Nanoparticle-sized powders have seen more and more use in many of today's applications. As particle size decreases, many properties change including the ability to embed the small particles in liquids and other media. With decreasing size, however, surface energy becomes more important and can dictate the final shape of the particle. In applications based on polar molecules attaching to the nanoparticle surface, the surface morphology can become a key design parameter. A nucleation and growth model has been constructed for truncated body-centered cubic derivative materials, along with an update to previously published work on face-centered cubic materials. The model shows that for (110)- and (111)-truncations of a cube with a specified surface energy for each surface, the critical nuclei and equilibrium growth shapes are the same, supporting the theory of self-similar growth that had only been mentioned previously, but never proven. In this analysis, saddle points play an important role in determining the critical nuclei for comparison with the equilibrium growth shapes.

AlGaN-based quantum well (QW) heterostructures grown by plasma-assisted molecular beam epitaxy on c-Al2O3 substrates have been studied. The high-temperature (785 °C) synthesis of AlN buffer layer nucleated by a migration-enhanced epitaxy and including several ultrathin GaN interlayers was the optimum approach for lowering the threading dislocations density down to 108–109 cm−2. High-angle annular dark-field scanning transmission electron microscopy (HAADF STEM) has revealed the step-like roughness of the AlN/Al2O3 interface. Also, the formation of Al-rich barriers induced by temperature-modulated epitaxy and the spontaneous compositional disordering have been found in the AlxGa1−xN (x > 0.6) barrier layers. The origin of these phenomena and their influence on parameters of the mid-UV stimulated emission observed in the QW heterostructures were discussed. The fine structure of the QWs formed by a submonolayer digital alloying technique has been displayed by HAADF STEM, and optical properties of the QW structures were studied by temperature- and time-dependent photoluminescence spectroscopy.

This article addresses recent advances in the application of microscopy techniques to characterize crystallization processes as they relate to biomineralization and bioinspired materials synthesis. In particular, we focus on studies aimed at revealing the role organic macromolecules and functionalized surfaces play in modulating the mechanisms of nucleation and growth. In nucleation studies, we explore the use of methods such as in situ transmission electron microscopy, atomic force microscopy, and cryogenic electron microscopy to delineate formation pathways, phase stabilization, and the competing effects of free energy and kinetic barriers. In growth studies, we emphasize understanding the interactions of macromolecular constituents with growing crystals and characterization of the internal structures of the resulting composite crystals using techniques such as electron tomography, atom probe tomography, and vibrational spectromicroscopy. Examples are drawn from both biological and bioinspired synthetic systems.

As the most abundant engineered material on Earth, concrete is essential to the physical infrastructure of all modern societies. There are no known materials that can replace concrete in terms of cost and availability. There are, however, environmental concerns, including the significant CO2 emissions associated with cement production, which create new incentives for university–industry collaboration to address concrete sustainability. Herein, we examine one aspect of this challenge—the translation of scientific understanding at the microscale into industrial innovation at the macroscale—by seeking improvements in cement-paste processing, performance, and sustainability through control of the mechanisms that govern microstructure development. Specifically, we consider modeling, simulation, and experimental advances in fracture, dissolution, precipitation, and hydration of cement paste precursors, as well as properties of the hardened cement paste within concrete. The aim of such studies is to optimize the chemical reactivity, mechanical performance, and other physical properties of cement paste to enable more sustainable processing routes for this ubiquitous material.

Silicon carbide nanowires (SiCNWs) (with diameters of tens of nanometer and aspect ratio well above 103), consisting of β-SiC one-dimensional single crystals wrapped in amorphous nitrogen-containing SiO2 sheaths, were efficiently synthesized in gram quantities by autogenous combustion synthesis using Si as a defluorination reagent of poly(tetrafluoroethylene). The combustion temperature was evaluated using the emission spectroscopy. Vapor–liquid–solid mechanism of a self-catalytic growth of the SiCNWs is proposed.

Development of phase composition in one-component, three-phase systems containing a liquid phase (melt) and two polymorphic solids has been discussed. Two types of polymorphic systems have been analyzed: enantiotropic systems composed of three thermodynamically stable phases and monotropic systems with two stable and one metastable phase. Detailed relations between transition rates, molecular characteristics, and external conditions have been derived. Simulation of isothermal crystallization of a model system has been performed and discussed.