Ecofriendly Synthesis of Waste-Tire-Derived Graphite Nanoflakes by a Low-Temperature Electrochemical Graphitization Process toward a Silicon-Based Anode with a High-Performance Lithium-Ion Battery.

Here, the successful transformation of graphitic carbon with a high degree of graphitization and a nanoflake structure from pyrolytic tire carbon black was demonstrated. First, amorphous carbon black with a porous structure was obtained after pyrolysis and simple preacid treatments. Subsequently, the carbon black was converted into a highly graphitic structure at a relatively low temperature (850 °C) through a facile electrochemical route using molten salt, which is ecofriendly and has high potential for large-scale graphitization compared to conventional incineration techniques. Moreover, we further improved the crystallinity and uniformity of the product simultaneously by directly mixing the metal oxide catalyst Fe2O3 with a carbon precursor. The mechanism of this metal-catalyzed electrochemical graphitization has been discussed in detail. To confirm their potential in practical applications, the as-prepared graphitized nanoflakes were used as conductive additives for silicon anodes in lithium-ion batteries, which showed a performance comparable to those utilizing commercial Super-P additives, exhibiting an initial Coulombic efficiency of approximately 79.7% and a high capacity retention of approximately 45.8% after 100 cycles with a reversible capacity of 1220 mAh g-1 at a current rate of 400 mA g-1. Hence, successfully recovered waste-tire-derived carbon black utilizing a low-temperature Fe2O3-catalyzed electrochemical process opens a pathway in low-temperature graphitization toward a sustainable value-added application in the field of energy storage.

Cultural Adaptation and Validation of Mullen Scales of Early Learning in Taiwanese children with Autism Spectrum Disorder, Global Developmental Delay, and Typically Developing Children.

BACKGROUND: The Mullen Scales of Early Learning (MSEL) is a standardized comprehensive developmental assessment tool for children aged 0-68 months. However, few Asia-based studies have explored cultural and linguistic adaptations of the MSEL or investigated its psychometric properties in populations with autism spectrum disorder (ASD). AIMS: This study evaluated the reliability and validity of the MSEL-Taiwan version (MSEL-T) for Taiwanese children with ASD, global developmental delay (GDD), and typical development (TD). METHODS AND PROCEDURES: The MSEL items were translated and modified according to the language and culture in Taiwan. In total, 191 children (ASD, 69; GDD, 36; and TD, 86) aged 19-68 months were assessed using the MSEL-T and Peabody Developmental Motor Scales 2 (PDMS-2) at enrollment, followed by the assessments of Vineland Adaptive Behavior Scale-Chinese version (VABS-C) at the age of 36 months or later. OUTCOMES AND RESULTS: All subscales were verified to have good interrater reliability and internal consistency, and subscale scores indicated moderate to high correlations with PDMS-2 and VABS-C scores. Significant differences in MSEL-T scores were observed between same-aged pairs of children with TD and GDD and between pairs of children with TD and ASD. CONCLUSIONS AND IMPLICATIONS: The findings provide evidence of validity and reliability of the MSEL-T. And it is suggested that the culturally and linguistically adapted MSEL-T is a good tool for the clinical assessment of children with and without ASD.

Multifunctional Ion-Sensitive Floating Gate Fin Field-Effect Transistor with Three-Dimensional Nanoseaweed Structure by Glancing Angle Deposition Technology.

A multifunctional ion-sensitive floating gate Fin field-effect transistor (ISFGFinFET) for hydrogen and sodium detection is demonstrated. The ISFGFinFET comprises a FGFET and a sensing film, both of which are used to detect and improve sensitivity. The sensitivity of the ISFGFinFET can be adjusted by modulating the coupling effect of the FG. A nanoseaweed structure is fabricated via glancing angle deposition (GLAD) technology to obtain a large sensing area to enhance the sensitivity for hydrogen ion detection. A sensitivity of 266 mV per pH can be obtained using a surface area of 3.28 mm2 . In terms of sodium ion detection, a calix[4]arene sensing film to monitor sodium ions, obtaining a Na+ sensitivity of 432.7 mV per pNa, is used. In addition, the ISFGFinFET demonstrates the functionality of multiple ions detection simultaneously. The sensor arrays composed of 3 × 3 pixels are demonstrated, each of which comprise of an FGFET sensor and a transistor. Furthermore, 16 × 16 arrays with a decoder and other peripheral circuits are constructed and simulated. The performance of the proposed ISFGFinFET is competitive with that of other state-of-the-art ion sensors.

Artificial Synapse Based on a 2D-SnO2 Memtransistor with Dynamically Tunable Analog Switching for Neuromorphic Computing.

A new type of two-dimensional (2D) SnO2 semiconductor-based gate-tunable memristor, that is, a memtransistor, an integrated device of a memristor and a transistor, was demonstrated to advance next-generation neuromorphic computing technology. The polycrystalline 2D-SnO2 memristors derived from a low-temperature and vacuum-free liquid metal process offer several interesting resistive switching properties such as excellent digital/analog resistive switching, multistate storage, and gate-tunability function of resistance switching states. Significantly, the gate tunability function that is not achievable in conventional two-terminal memristors provides the capability to implement heterosynaptic analog switching by regulating gate bias for enabling complex neuromorphic learning. We successfully demonstrated that the gate-tunable synaptic device dynamically modulated the analog switching behavior with good linearity and an improved conductance change ratio for high recognition accuracy learning. The presented gate-tunable 2D-oxide memtransistor will advance neuromorphic device technology and open up new opportunities to design learning schemes with an extra degree of freedom.

In Situ Current-Accelerated Phase Cycling with Metallic and Semiconducting Switching in Copper Nanobelts at Room Temperature.

Here, a current-accelerated phase cycling by an in situ current-induced oxidation process was demonstrated to reversibly switch the local metallic Cu and semiconducting Cu2O phases of patterned polycrystalline copper nanobelts. Once the Cu nanobelts were applied by a direct-current bias of ∼0.5 to 1 V in air with opposite polarities, the resistance between several hundred ohms and more than MΩ can be manipulated. In practice, the thickness of 60 nm with a moderate grain size inhibiting both electromigration and permanent oxidation is the optimized condition for reversible switching when the oxygen supply is sufficient. More than 40% of the copper localized beneath the positively biased electrode was oxidized assisted by the Joule heating, blocking the current flow. On the contrary, the reduction reaction of Cu2O was activated by the thermally assisted electromigration of Cu atoms penetrating the interlayer at the reverse bias. Finally, based on a high on/off ratio, the fast switching and the scalable production, reusable feasibility based on copper nanobelts such as the memristor array was demonstrated.

Three-Dimensional Molybdenum Diselenide Helical Nanorod Arrays for High-Performance Aluminum-Ion Batteries.

The rechargeable aluminum-ion battery (AIB) is a promising candidate for next-generation high-performance batteries, but its cathode materials require more development to improve their capacity and cycling life. We have demonstrated the growth of MoSe2 three-dimensional helical nanorod arrays on a polyimide substrate by the deposition of Mo helical nanorod arrays followed by a low-temperature plasma-assisted selenization process to form novel cathodes for AIBs. The binder-free 3D MoSe2-based AIB shows a high specific capacity of 753 mAh g-1 at a current density of 0.3 A g-1 and can maintain a high specific capacity of 138 mAh g-1 at a current density of 5 A g-1 with 10 000 cycles. Ex situ Raman, XPS, and TEM characterization results of the electrodes under different states confirm the reversible alloying conversion and intercalation hybrid mechanism during the discharge and charge cycles. All possible chemical reactions were proposed by the electrochemical curves and characterization. Further exploratory works on interdigital flexible AIBs and stretchable AIBs were demonstrated, exhibiting a steady output capacity under different bending and stretching states. This method provides a controllable strategy for selenide nanostructure-based AIBs for use in future applications of energy-storage devices in flexible and wearable electronics.

High-Performance Rechargeable Aluminum-Selenium Battery with a New Deep Eutectic Solvent Electrolyte: Thiourea-AlCl3.

Aluminum-sulfur batteries (ASBs) have attracted substantial interest due to their high theoretical specific energy density, low cost, and environmental friendliness, while the traditional sulfur cathode and ionic liquid have very fast capacity decay, limiting cycling performance because of the sluggishly electrochemical reaction and side reactions with the electrolyte. Herein, we demonstrate, for the first time, excellent rechargeable aluminum-selenium batteries (ASeBs) using a new deep eutectic solvent, thiourea-AlCl3, as an electrolyte and Se nanowires grown directly on a flexible carbon cloth substrate (Se NWs@CC) by a low-temperature selenization process as a cathode. Selenium (Se) is a chemical analogue of sulfur with higher electronic conductivity and lower ionization potential that can improve the battery kinetics on the sluggishly electrochemical reaction and the reduction of the polarization where the thiourea-AlCl3 electrolyte can stabilize the side reaction during the reversible conversion reaction of Al-Se alloying processes during the charge-discharge process, yielding a high specific capacity of 260 mAh g-1 at 50 mA g-1 and a long cycling life of 100 times with a high Coulombic efficiency of nearly 93% at 100 mA g-1. The working mechanism based on the reversible conversion reaction of the Al-Se alloying processes, confirmed by the ex situ Raman, XRD, and XPS measurements, was proposed. This work provides new insights into the development of rechargeable aluminum-chalcogenide (S, Se, and Te) batteries.

An indoor light-activated 3D cone-shaped MoS2 bilayer-based NO gas sensor with PPb-level detection at room-temperature.

Utilization of light to boost the performance of gas sensors allows us to operate sensor devices at room temperature. Here, we, for the first time, demonstrated an indoor light-activated 3D cone-shaped MoS2 bilayer-based NO gas sensor with ppb-level detection operated at room-temperature. Large-area cone-shaped (CS)-MoS2 bilayers were grown by depositing 2 nm-thick MoO3 layers on a 2'' three-dimensional (3D) cone-patterned sapphire substrate (CPSS) followed by a sulfurization process via chemical vapor deposition. Because the exposed area of MoS2 bilayers is increased by 30%, the CS-MoS2 gas sensor (GS) demonstrated excellent performance with a response of ∼470% and a fast response time of ∼25 s after exposure to 1 ppm of NO gas illuminated by ultraviolet (UV) light with a wavelength of 365 nm. Such extraordinary performance at room temperature is attributed to the enhanced light absorption because of the light scattering effect caused by the 3D configuration and photo-desorption induced by UV illumination. For NO concentrations ranging from 2 ppm down to 0.06 ppm, the CS-MoS2 GS demonstrated a stable sensing behavior with a high response and fast response time (470% and 25 s at 2 ppm NO) because of the light absorption enhanced by the 3D structure and photo-desorption under constant UV illumination. The CS-MoS2 GS exhibits a high sensitivity (∼189.2 R% ppm-1), allowing the detection of NO gas at 0.06 ppm in 130 s. In addition, the 3D cone-shaped structure prolonged the presence of sulfur vapor around MoO3, allowing MoO3 to react with sulfur completely. Furthermore, the CS-MoS2 GS using an indoor lighting to detect NO gas at room temperature was demonstrated for the first time where the CS-MoS2 GS exhibits a stable cycling behavior with a high response (165% at 1 ppm NO) in 50 s; for concentration as low as ∼0.06 ppm, the response of ∼75% in 150 s can be achieved.

Environmentally and Mechanically Stable Selenium 1D/2D Hybrid Structures for Broad-Range Photoresponse from Ultraviolet to Infrared Wavelengths.

Selenium (Se) is one of the potential candidates as photodetector because of its outstanding properties such as high photoconductivity (∼8 × 104 S cm-1), piezoelectricity, thermoelectricity, and nonlinear optical responses. Solution phase synthesis becomes an efficient way to produce Se, but a contamination issue that could deteriorate the electric characteristic of Se should be taken into account. In this work, a facile, controllable approach of synthesizing Se nanowires (NWs)/films via a plasma-assisted growth process was demonstrated at the low substrate temperature of 100 °C. The detailed formation mechanisms of nanowires arrays to thin films at different plasma powers were investigated. Moreover, indium (In) layer was used to enhance the adhesive strength with 50% improvement on a SiO2/Si substrate by mechanical interlocking and surface alloying between Se and In layers, indicating great tolerance for mechanical stress for future wearable devices applications. Furthermore, the direct growth of Se NWs/films on a poly(ethylene terephthalate) substrate was demonstrated, exhibiting a visible to broad infrared detection ranges from 405 to 1555 nm with a high on/off ratio of ∼700 as well as the fast response time less than 25 ms. In addition, the devices exhibited fascinating stability in the atmosphere over one month.

Wafer Scale Phase-Engineered 1T- and 2H-MoSe2 /Mo Core-Shell 3D-Hierarchical Nanostructures toward Efficient Electrocatalytic Hydrogen Evolution Reaction.

The necessity for new sources for greener and cleaner energy production to replace the existing ones has been increasingly growing in recent years. Of those new sources, the hydrogen evolution reaction has a large potential. In this work, for the first time, MoSe2 /Mo core-shell 3D-hierarchical nanostructures are created, which are derived from the Mo 3D-hierarchical nanostructures through a low-temperature plasma-assisted selenization process with controlled shapes grown by a glancing angle deposition system.

Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis.

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.

Facile Growth of Cu2ZnSnS4 Thin-Film by One-Step Pulsed Hybrid Electrophoretic and Electroplating Deposition.

The use of costly and rare metals such as indium and gallium in Cu(In,Ga)Se2 (CIGS) based solar cells has motivated research into the use of Cu2ZnSnS4 (CZTS) as a suitable replacement due to its non-toxicity, abundance of compositional elements and excellent optical properties (1.5 eV direct band gap and absorption coefficient of ~10(4) cm(-1)). In this study, we demonstrate a one-step pulsed hybrid electrodeposition method (PHED), which combines electrophoretic and electroplating deposition to deposit uniform CZTS thin-films. Through careful analysis and optimization, we are able to demonstrate CZTS solar cells with the VOC, JSC, FF and η of 350 mV, 3.90 mA/cm(2), 0.43 and 0.59%, respectively.

Enhanced Conversion Efficiency of Cu(In,Ga)Se2 Solar Cells via Electrochemical Passivation Treatment.

Defect control in Cu(In,Ga)Se2 (CIGS) materials, no matter what the defect type or density, is a significant issue, correlating directly to PV performance. These defects act as recombination centers and can be briefly categorized into interface recombination and Shockley-Read-Hall (SRH) recombination, both of which can lead to reduced PV performance. Here, we introduce an electrochemical passivation treatment for CIGS films that can lower the oxygen concentration at the CIGS surface as observed by X-ray photoelectron spectrometer analysis. Temperature-dependent J-V characteristics of CIGS solar cells reveal that interface recombination is suppressed and an improved rollover condition can be achieved following our electrochemical treatment. As a result, the surface defects are passivated, and the power conversion efficiency performance of the solar cell devices can be enhanced from 4.73 to 7.75%.

Large-scale micro- and nanopatterns of Cu(In,Ga)Se2 thin film solar cells by mold-assisted chemical-etching process.

A reactive mold-assisted chemical etching (MACE) process through an easy-to-make agarose stamp soaked in bromine methanol etchant to rapidly imprint larger area micro- and nanoarrays on CIGS substrates was demonstrated. Interestingly, by using the agarose stamp during the MACE process with and without additive containing oil and triton, CIGS microdome and microhole arrays can be formed on the CIGS substrate. Detailed formation mechanisms of microstructures and the chemical composition variation after the etching process were investigated. In addition, various microand nanostructures were also demonstrated by this universal approach. The microstructure arrays integrated into standard CIGS solar cells with thinner thickness can still achieve an efficiency of 11.22%, yielding an enhanced efficiency of ∼18% compared with that of their planar counterpart due to an excellent absorption behavior confirmed by the simulation results, which opens up a promising way for the realization of high-efficiency micro- or nanostructured thin-film solar cells. Finally, the complete dissolution of agarose stamp into hot water demonstrates an environmentally friendly method by the mold-assisted chemical etching process through an easy-to-make agarose stamp.

Extraction of heavy metals from contaminated soil by Cinnamomum camphora.

83 acres of rice paddy fields in Taoyuan county, Taiwan, were polluted by cadmium (Cd), chromium (Cr) and copper (Cu) through a nearby irrigation channel, and rice plantation was ceased in 1987. Camphor trees (Cinnamomum camphora) have been planted in 2 acre of the above fields since 1991. Heavy metal accumulation of roots, leaves, branches and heartwood of camphor trees were analyzed during 20-year afforestation. Averaged Cd contents of the roots were found larger than the ones of the branches, leaves, sapwood and heartwood of camphor trees growing in three polluted plots. Averaged diameters at breast height (DBH) of the planted camphor trees were 13-15 cm. Cd pollution did not significantly impact the growth of camphor trees, as similar DBH's were found from both polluted and control sites. Annual growths of DBH were from 0.63 to 0.77 cm year(-1). Planting camphor trees sequestered 68.8 ton biomass per acre. During 20-year period, 0.69-1.98 ton C year(-1) ha(-1) were sequestered on three polluted plots. The above numbers exceeded IPCC LULUCF reference values 0.31-0.53 ton C year(-1) ha(-1) for activities at forest lands.

Single CuO(x) nanowire memristor: forming-free resistive switching behavior.

CuOx nanowires were synthesized by a low-cost and large-scale electrochemical process with AAO membranes at room temperature and its resistive switching has been demonstrated. The switching characteristic exhibits forming-free and low electric-field switching operation due to coexistence of significant amount of defects and Cu nanocrystals in the partially oxidized nanowires. The detailed resistive switching characteristics of CuOx nanowire systems have been investigated and possible switching mechanisms are systematically proposed based on the microstructural and chemical analysis via transmission electron microscopy.

An in situ approach for facile fabrication of robust and scalable SERS substrates.

The widespread implementation of surface enhanced Raman scattering (SERS) techniques for chemical and biological detection requires an inexpensive, yet robust SERS substrate with high sensitivity and reproducibility. To that end, we present a facile method to fabricate plasmonic SERS substrates with well-distributed SERS "hot spots" on a large scale with reproducible SERS enhancement factors of ∼10(8) for the Raman probe molecule 4-aminobenzenethiol (4-ABT). The SERS enhancement is attributed to the synergistic interactions between the strong plasmonic coupling among the assembled Au NPs and the structure-associated tip enhancement. Additionally, these mechanically-flexible substrates exhibit remarkably reproducible SERS signals, demonstrating the merits of our methodology. Our approach illustrates the potential opportunities for fabricating robust, commercially-viable SERS substrates with well-distributed "hot spots" on a large scale while avoiding costly vacuum deposition technologies.

Surface plasmon-driven water reduction: gold nanoparticle size matters.

Water reduction under two different visible-light ranges (λ > 400 nm and λ > 435 nm) was investigated in gold-loaded titanium dioxide (Au-TiO2) heterostructures with different sizes of Au nanoparticles (NPs). Our study clearly demonstrates the essential role played by Au NP size in plasmon-driven H2O reduction and reveals two distinct mechanisms to clarify visible-light photocatalytic activity under different excitation conditions. The size of the Au NP governs the efficiency of plasmon-mediated electron transfer and plays a critical role in determining the reduction potentials of the electrons transferred to the TiO2 conduction band. Our discovery provides a facile method of manipulating photocatalytic activity simply by varying the Au NP size and is expected to greatly facilitate the design of suitable plasmonic photocatalysts for solar-to-fuel energy conversion.

Large scale and orientation-controllable nanotip structures on CuInS2, Cu(In,Ga)S2, CuInSe2, and Cu(In,Ga)Se2 by low energy ion beam bombardment process: growth and characterization.

One-step facile methodology to create nanotip arrays on chalcopyrite materials (such as CuInS2, Cu(In,Ga)S2, CuInSe2, and Cu(In,Ga)Se2) via a low energy ion beam bombardment process has been demonstrated. The mechanism of formation for nanotip arrays has been proposed by sputtering yields of metals and reduction of metals induced by the ion beam bombardment process. The optical reflectance of these chalcopyrite nanotip arrays has been characterized by UV-vis spectrophotometer and the efficient light-trapping effect has been observed. Large scale (∼4'') and high density (10(10) tips/cm(2)) of chalcopyrite nanotip arrays have been obtained by using low ion energy (< 1 kV), short processing duration (< 30 min), and template-free. Besides, orientation and length of these chalcopyrite nanotip arrays are controllable. Our results can be the guide for other nanostructured materials fabrication by ion sputtering and are available for industrial production as well.

Non-antireflective scheme for efficiency enhancement of Cu(In,Ga)Se2 nanotip array solar cells.

We present systematic works in characterization of CIGS nanotip arrays (CIGS NTRs). CIGS NTRs are obtained by a one-step ion-milling process by a direct-sputtering process of CIGS thin films (CIGS TF) without a postselenization process. At the surface of CIGS NTRs, a region extending to 100 nm in depth with a lower copper concentration compared to that of CIGS TF has been discovered. After KCN washing, removal of secondary phases can be achieved and a layer with abundant copper vacancy (V(Cu)) was left. Such compositional changes can be a benefit for a CIGS solar cell by promoting formation of Cd-occupied Cu sites (Cd(Cu)) at the CdS/CIGS interface and creates a type-inversion layer to enhance interface passivation and carrier extraction. The raised V(Cu) concentration and enhanced Cd diffusion in CIGS NTRs have been verified by energy dispersive spectrometry. Strengthened adhesion of Al:ZnO (AZO) thin film on CIGS NTRs capped with CdS has also been observed in SEM images and can explain the suppressed series resistance of the device with CIGS NTRs. Those improvements in electrical characteristics are the main factors for efficiency enhancement rather than antireflection.