Single-Crystal Ferroelectric-Based (K,Na)NbO3 Microcuboid/CuO Nanodot Heterostructures with Enhanced Photo-Piezocatalytic Activity.

Developing single-crystal-based heterostructured ferroelectrics with high-performance photo-piezocatalytic activity is highly desirable to utilize large piezopotentials and more reactive charges that can trigger the desired redox reactions. To that end, a single-crystal-based (K,Na)NbO3 (KNN) microcuboid/CuO nanodot heterostructure with enhanced photo-piezocataytic activity, prepared using a facile strategy that leveraged the synergy between heterojunction formation and an intense single-crystal-based piezoelectric effect, is reported herein. The catalytic rhodamine B degrading activity of KNN/CuO is investigated under light irradiation, ultrasonication, or co-excitation with both stimulations. Compared to polycrystalline KNN powders and bare KNN single-crystals, single-crystal-based KNN/CuO exhibits a higher piezocurrent density and an optimal energy band structure, resulting in 5.23 and 2.37 times higher piezocatalytic degradation activities, respectively. Furthermore, the maximum photo-piezocatalytic rate constant (≈0.093 min-1 ) of KNN/CuO under 25 min ultrasonication and light irradiation is superior to that of other KNN-based catalysts, and 1.6 and 48.6 times higher than individual piezocatalytic and photocatalytic reaction rate constants, respectively. The excellent photo-piezocatalytic activity is attributed to the enhanced charge-carrier separation and proper alignment of band structure to the required redox levels by the appropriate p-n heterojunction and high piezoelectric potential. This report provides useful insight into the relationships between heterojunctions, piezoelectric responses, and catalytic mechanisms for single-crystal-based heterostructured catalysts.

Molten-Salt Processed Potassium Sodium Niobate Single-Crystal Microcuboids with Dislocation-Induced Nanodomain Structures and Relaxor Ferroelectric Behavior.

We herein report a facile molten-salt synthetic strategy to prepare transparent and uniform Li, Ba-doped (K,Na)NbO3 (KNN) single-crystal microcuboids (∼80 µm). By controlling the degree of supersaturation, different growth modes were found and the single-crystal microcuboids were synthesized via island-like oriented attachment of KNN particles onto the growing surface. The distinct relaxor ferroelectric (RFE) properties were achieved in the single-crystal microcuboids, which were different from the normal ferroelectric (FE) properties found in their KNN ceramic counterparts prepared through a solid-state reaction using the same initial precursors. The RFE properties were realized by dislocation-induced nanodomain formation during oriented attachment growth of single-crystal microcuboids, which is different from the current strategies to derive the nanodomains by the local compositional inhomogeneity or the application of an electric field. The dislocations served as nucleation sites for ferroelectric domain walls and block the growth of domains. The KNN single-crystal microcuboids exhibited a higher effective piezoelectric coefficient (∼459 pm/V) compared to that of the bulk KNN ceramic counterpart (∼90 pm/V) and showed the broad diffuse maxima in the temperature dependence dielectric permittivity. The high maximum polarization (69.6 µC/cm2) at a relatively low electric field (30 kV/cm) was beneficial for energy storage applications. Furthermore, the KNN-based transparent, flexible pressure sensor directly monitored the mechanical motion of human activity without any external electric power. This study provides insights and synthetic strategies of single-crystal RFE microcuboids for other different perovskites, in which nanodomain structures are primarily imposed by their chemical composition.

Supraparticle Engineering for Highly Dense Microspheres: Yttria-Stabilized Zirconia with Adjustable Micromechanical Properties.

Various supraparticles have been extensively studied owing to their excellent catalytic properties that are attributed to their inherent porous structure; however, their mechanical properties have not garnered attention owing to their less dense structure. We demonstrate a rational approach for fabricating assembled supraparticles and, subsequently, highly dense microspheres. In addition, 3 mol % yttria-stabilized zirconia (3YSZ) and alumina particles were selected as building blocks and assembled into higher-order architectures using a droplet-based template method (spray drying) for validation with proof-of-concept. Moreover, structural features such as density, size, sphericity, and morphology of supraparticles were controlled by adjusting the competing kinetics occurring between the assembly of building blocks and evaporation of the solvent in the droplets. The preparatory aqueous suspension and process parameters were optimized as well. A detailed understanding of the formation mechanism facilitated the yield of tailor-made supraparticles and, thereafter, highly dense microspheres (approximate relative density = 99%) with excellent sphericity (>98%) via heat treatment. The microspheres displayed highest hardness (26.77 GPa) and superior elastic modulus (210.19 GPa) compared with the mechanical properties of the 3YSZ samples reported to date. Ultimately, the proposed supraparticle engineering provided insight for controlling the structural features and resultant micromechanical properties, which widely extends the applicability of supraparticle-based functional materials for practical purposes that require materials with high density and excellent mechanical properties.

Selective Phase Control of Dopant-Free Potassium Sodium Niobate Perovskites in Solution.

As one of the perovskite families, potassium sodium niobates (K1-xNax)NbO3 (KNN) have been gaining tremendous attention due to their various functional properties which can be largely determined by their crystallographic phase and composition. However, a selective evolution of different phases for KNN with controlled composition can be difficult to achieve, especially in solution chemical synthesis because of its strong tendency to stabilize into orthorhombic phase at conventional synthetic temperature. We herein developed a facile solution approach to control the phase and composition of dopant-free KNN particles selectively through the modification of reaction parameters. A conventional hydrothermal synthesis method yielded orthorhombic KNN particles, while the monoclinic phase, which has never been observed in a bulk counterpart, was kinetically generated by the compositional modification of an intermediate phase under a high-intensity ultrasound irradiation. Cubic KNN particles were stabilized when ethylene glycol was used as a co-solvent together with deionized water through bonding between ethylene glycol molecules and the surface of the KNN. Composite-structured piezoelectric harvesters were fabricated using each phase of KNN particles and the ß-phase poly(vinylidene fluoride-co-trifluoroethylene) polymer. Maximum output power was found for the harvester containing orthorhombic KNN particles. This facile synthetic methodology could pave a new pathway for fabricating numerous phase-controlled materials.

A Comparison Study of Fatigue Behavior of Hard and Soft Piezoelectric Single Crystal Macro-Fiber Composites for Vibration Energy Harvesting.

Designing a piezoelectric energy harvester (PEH) with high power density and high fatigue resistance is essential for the successful replacement of the currently using batteries in structural health monitoring (SHM) systems. Among the various designs, the PEH comprising of a cantilever structure as a passive layer and piezoelectric single crystal-based fiber composites (SFC) as an active layer showed excellent performance due to its high electromechanical properties and dynamic flexibilities that are suitable for low frequency vibrations. In the present study, an effort was made to investigate the reliable performance of hard and soft SFC based PEHs. The base acceleration of both PEHs is held at 7 m/s2 and the frequency of excitation is tuned to their resonant frequency (fr) and then the output power (Prms) is monitored for 107 fatigue cycles. The effect of fatigue cycles on the output voltage, vibration displacement, dielectric, and ferroelectric properties of PEHs was analyzed. It was noticed that fatigue-induced performance degradation is more prominent in soft SFC-based PEH (SS-PEH) than in hard SFC-based PEH (HS-PEH). The HS-PEH showed a slight degradation in the output power due to a shift in fr, however, no degradation in the maximum power was noticed, in fact, dielectric and ferroelectric properties were improved even after 107 vibration cycles. In this context, the present study provides a pathway to consider the fatigue life of piezoelectric material for the designing of PEH to be used at resonant conditions for long-term operation.

Enhancement of Magnetoelectric Conversion Achieved by Optimization of Interfacial Adhesion Layer in Laminate Composites.

We report the effect of epoxy adhesion layers with different mechanical or physical property on a magnetoelectric (ME) composite laminate composed of FeBSi alloy (Metglas)/single-crystal Pb(Mg1/3Nb2/3)O3-Pb(Zr,Ti)O3/Metglas to achieve an improved ME conversion performance. Through theoretical simulation, it was revealed that the Young's modulus and the thickness of interfacial adhesives were major parameters that influence the conversion efficiency in ME composites. In the experimental evaluation, we utilized three epoxy materials with a distinct Young's modulus and adjusted the average thickness of the adhesion layers to optimize the ME conversion. The experimental results show that a thin epoxy layer with a high Young's modulus provided the best performance in the inorganic-based ME conversion process. By tailoring the interfacial adhesion property, the ME laminate generated a high conversion coefficient of 328.8 V/(cm Oe), with a mechanical quality factor of 132.0 at the resonance mode. Moreover, we demonstrated a highly sensitive alternating current magnetic field sensor that had a detection resolution below 10 pT. The optimization of the epoxy layers in the ME laminate composite provided significant enhancement of the ME response in a simple manner.

Dimensional and compositional change of 1D chalcogen nanostructures leading to tunable localized surface plasmon resonances.

As part of the oxygen family, chalcogen (Se, Te) nanostructures have been considered important elements for various practical fields and further exploited to constitute metal chalcogenides for each targeted application. Here, we report a controlled synthesis of well-defined one-dimensional chalcogen nanostructures such as nanowries, nanorods, and nanotubes by controlling reduction reaction rate to fine-tune the dimension and composition of the products. Tunable optical properties (localized surface plasmon resonances) of these chalcogen nanostructures are observed depending on their morphological, dimensional, and compositional variation.

Catalytic topological insulator Bi2Se3 nanoparticles for invivo protection against ionizing radiation.

Bi2Se3 nanoparticles (NPs) have attracted wide interests in biological and medical applications. Layer-like Bi2Se3 with high active surface area is promising for free radical scavenging. Here, we extended the medical applications of Bi2Se3 NPs further to in vivo protection against ionizing radiation based on their superior antioxidant activities and electrocatalytic properties. It was found that Bi2Se3 NPs can significantly increase the surviving fraction of mice after exposure of high-energy radiation of gamma ray. Additionally, the Bi2Se3 NPs can help to recover radiation-lowered red blood cell counts, white blood cell counts and platelet levels. Further investigations revealed that Bi2Se3 NPs behaved as functional free radical scavengers and significantly decreased the level of methylenedioxyamphetamine. In vivo toxicity studies showed that Bi2Se3 NPs did not cause significant side effects in panels of blood chemistry, clinical biochemistry and pathology.

Synthesis of Multishell Nanoplates by Consecutive Epitaxial Growth of Bi2Se3 and Bi2Te3 Nanoplates and Enhanced Thermoelectric Properties.

We herein demonstrate the successive epitaxial growth of Bi2Te3 and Bi2Se3 on seed nanoplates for the scalable synthesis of heterostructured nanoplates (Bi2Se3@Bi2Te3) and multishell nanoplates (Bi2Se3@Bi2Te3@Bi2Se3, Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3). The relative dimensions of the constituting layers are controllable via the molar ratios of the precursors added to the seed nanoplate solution. Reduction of the precursors produces nanoparticles that attach preferentially to the sides of the seed nanoplates. Once attached, the nanoparticles reorganize epitaxially on the seed crystal lattices to form single-crystalline core-shell nanoplates. The nanoplates, initially 100 nm wide, grew laterally to 620 nm in the multishell structure, while their thickness increased more moderately, from 5 to 20 nm. The nanoplates were pelletized into bulk samples by spark plasma sintering and their thermoelectric properties are compared. A peak thermoelectric figure of merit (ZT) ∼0.71 was obtained at 450 K for the bulk of Bi2Se3@Bi2Te3 nanoplates by simultaneous modulation of electronic and thermal transport in the presence of highly dense grain and phase boundaries.

Nonstoichiometric nucleation and growth of multicomponent nanocrystals in solution.

The ability to assemble nanoscale functional building blocks is a useful and modular way for scientists to design valuable materials with specific physical and chemical properties. Chemists expect multicomponent, heterostructured nanocrystals to show unique electrical, thermal, and optical properties not seen in homogeneous, single-phase nanocrystals. Although researchers have made remarkable advances in heterogeneous nucleation and growth, design of synthetic conditions for obtaining nanocrystals with a target composition and shape is still a big challenge. There are several outstanding issues that chemists need to address before they can successfully carry out the design-based synthesis of multicomponent nanocrystals. For instance, small changes in the reaction parameters, such as the precursor, solvent, surfactant, reducing agent, and the reaction temperature, often result in changes in the structure and chemical composition of the final product. Although scientists do not fully understand the mechanisms underlying the nucleation and growth processes involved in the synthesis of these multicomponent nanocrystals, recent progress in understanding of the thermodynamic and kinetic factors have improved our control over their final structure and chemical composition. In this Account, we summarize our recent advances in understanding of the nucleation and growth mechanisms involved in the solution-based synthesis of multicomponent nanocrystals. We also discuss the various challenges encountered in their synthesis, emphasizing what still needs special consideration. We first discuss the three different nucleation paths from a thermodynamics perspective: amorphous nucleation, crystalline nucleation, and two-step nucleation. Amorphous nucleation and two-step nucleation involve the generation of nonstoichiometric nuclei. We initiate this process mainly by introducing an imbalance in the concentrations of the reduced elements. When the nonstoichiometric nuclei grow, we can add secondary elements to the growing nonstoichiometric nuclei. This leads to either the physical deposition or atomic mixture formation through the diffusion and rearrangement of constituents. The processes of mixture formation and the physical deposition of the secondary constituent element also compete and determine the shape and chemical composition of the final product. If the free energy change by mixture formation is positive (ΔGAB ≥ 0), physical deposition takes place predominantly, and the spreading coefficient (S) determines the structure of the nanocrystals. However, when mixture formation is highly spontaneous (ΔGAB < -ξ), the chemical composition of the final product is usually stoichiometric, and its shape then depends on the size of the primary nanocrystals. When the mixture formation and physical deposition are in competition (-ξ ≤ ΔGAB < 0), as commonly seen for many nanoalloy systems, both the chemical composition and the structure are determined by the size of the primary nanocrystals as well as the degree of mixture formation at the interface of the constituent components. Finally, we discuss the challenges and caveats that one needs to take into account when synthesizing multicomponent nanocrystals.

Growth of long triisopropylsilylethynyl pentacene (TIPS-PEN) nanofibrils in a polymer thin film during spin-coating.

This study demonstrates the growth of long triisopropylsilyethynyl pentacene (TIPS-PEN) nanofibrils in a thin film of a crystalline polymer, poly(ε-caprolactone) (PCL). During spin-coating, TIPS-PEN molecules are locally extracted around the PCL grain boundaries and they crystallize into [010] direction forming long nanofibrils. Molecular weight of PCL and weight fraction (α) of TIPS-PEN in PCL matrix are key factors to the growth of nanofibrils. Long high-quality TIPS-PEN nanofibrils are obtained with high-molecular-weight PCL and at the α values in the range of 0.03-0.1. The long nanofibrils are used as an active layer in a field-effect organic transistor.

Surfactant-free scalable synthesis of Bi2 Te3 and Bi2Se3 nanoflakes and enhanced thermoelectric properties of their nanocomposites.

Surfactant-free nanoflakes of n-type Bi2 Te3 and Bi2 Se3 are synthesized in high yields. Their suspensions are mixed to create nanocomposites with heterostructured nanograins. A maximum ZT (0.7 at 400 K) is achieved with a broad content of 10-15% Bi2 Se3 in the nanocomposites.

Highly stretchable electric circuits from a composite material of silver nanoparticles and elastomeric fibres.

Conductive electrodes and electric circuits that can remain active and electrically stable under large mechanical deformations are highly desirable for applications such as flexible displays, field-effect transistors, energy-related devices, smart clothing and actuators. However, high conductivity and stretchability seem to be mutually exclusive parameters. The most promising solution to this problem has been to use one-dimensional nanostructures such as carbon nanotubes and metal nanowires coated on a stretchable fabric, metal stripes with a wavy geometry, composite elastomers embedding conductive fillers and interpenetrating networks of a liquid metal and rubber. At present, the conductivity values at large strains remain too low to satisfy requirements for practical applications. Moreover, the ability to make arbitrary patterns over large areas is also desirable. Here, we introduce a conductive composite mat of silver nanoparticles and rubber fibres that allows the formation of highly stretchable circuits through a fabrication process that is compatible with any substrate and scalable for large-area applications. A silver nanoparticle precursor is absorbed in electrospun poly (styrene-block-butadiene-block-styrene) (SBS) rubber fibres and then converted into silver nanoparticles directly in the fibre mat. Percolation of the silver nanoparticles inside the fibres leads to a high bulk conductivity, which is preserved at large deformations (σ ≈ 2,200 S cm(-1) at 100% strain for a 150-µm-thick mat). We design electric circuits directly on the electrospun fibre mat by nozzle printing, inkjet printing and spray printing of the precursor solution and fabricate a highly stretchable antenna, a strain sensor and a highly stretchable light-emitting diode as examples of applications.

Quick, controlled synthesis of ultrathin Bi2Se3 nanodiscs and nanosheets.

Ultrathin (4-6 nm) single-crystal Bi(2)Se(3) nanodiscs and nanosheets were synthesized through a simple and quick solution process. The growth mechanism was investigated in detail. Crystal seeds grew via 2D self-attachment of small nanoparticles followed by epitaxial recrystallization into single crystals. The lateral dimension of the nanodiscs increased and their shape changed from circles to hexagons as the reaction temperature increased. Positively charged polymer surfactants greatly enlarged the lateral dimension to produce nanosheets with uniform thickness.

Surfactant-free CuInSe2 nanocrystals transformed from In2Se3 nanoparticles and their application for a flexible UV photodetector.

In(2)Se(3) nanoparticles were synthesized in an aqueous solution without using any surfactant and then chemically transformed into CuInSe(2) nanocrystals. The transformation was thermodynamically favorable and fast. The 93% production yield in mild reaction conditions allowed mass production of the CuInSe(2) nanocrystals. By the virtue of the surface charges, the CuInSe(2) nanocrystals were well dispersed in polar solvents. The surfactant-free nanocrystals enabled the formation of semiconducting CuInSe(2) films on a flexible polymer substrate without any thermal treatment. We took advantage of this to fabricate a flexible UV photodetector. The current and sensitivity of the devices could be improved by utilizing CuInSe(2) nanocrystals annealed at 160 °C in the reaction batch. On bending test, the detection sensitivity remained the same until the bending radius was reduced down to 4 mm. The dynamic response of the film device was stable and reproducible during light illumination (350 nm).

Understanding the epitaxial growth of SexTey@Te core-shell nanorods and the generation of periodic defects.

This study demonstrates solution-processed epitaxial growth of Te on Se(x)Te(y) nanorods and the generation of periodic defects in the core. We investigated Se(x)Te(y)@Te core-shell nanorods with a diameter of 40-50 nm and a length of 600-700 nm. In spite of a large lattice mismatch between the Se(x)Te(y) core and the Te shell, the soft character of the core and the shell at a high reaction temperature allowed epitaxial growth of Te on the Se(x)Te(y) nanorods. During the cooling process to room temperature (below the glass transition temperatures), the lattice mismatch between the core and the shell led to homogeneous stress along the epitaxial interface so that periodic defects were generated in the core.