Uniformly dispersed ruthenium nanoparticles on porous carbon from coffee waste outperform platinum for hydrogen evolution reaction in alkaline media.

Biowaste-derived carbon materials are a sustainable, environmentally friendly, and cost-effective way to create valuable materials. Activated carbon can be a supporting material for electrocatalysts because of its large specific surface area and porosity. However, activated carbon has low catalytic activity and needs to be functionalized with heteroatoms, metals, and combinations to improve conductivity and catalytic activity. Ruthenium (Ru) catalysts have great potential to replace bench market catalysts in hydrogen evolution reaction (HER) applications due to their similar hydrogen bond strength and relatively lower price. This study reports on the synthesis and characterizations of carbon-supported Ru catalysts with large surface areas (~ 1171 m2 g-1) derived from coffee waste. The uniformly dispersed Ru nanoparticles on the porous carbon has excellent electrocatalytic activity and outperformed the commercial catalyst platinum on carbon (Pt/C) toward the HER. As-synthesized catalyst needed only 27 mV to reach a current density of 10 mA cm-2, 58.4 mV dec-1 Tafel slope, and excellent long-term stability. Considering these results, the Ru nanoparticles on coffee waste-derived porous carbon can be utilized as excellent material that can replace platinum-based catalysts for the HER and contribute to the development of eco-friendly and low-cost electrocatalyst materials.

The self-annealing phenomenon of electrodeposited nano-twin copper with high defect density.

Electroplated copper was prepared under typical conditions and a high defect density to study the effect of the defects on its self-annealing phenomenon. Two conditions, grain growth and stress relaxation during self-annealing, were analyzed with electron backscattered diffraction and a high-resolution X-ray diffractometer. Abnormal grain growth was observed in both conditions; however, the grown crystal orientation differed. The direction and relative rate at which abnormal grain growth proceeds were specified through textured orientation, and the self-annealing mechanism was studied by observing the residual stress changes over time in the films using the sin2Ψ method.

Capacitive humidity sensing properties of freestanding bendable porous SiO2/Si thin films.

The fabrication of freestanding bendable films without polymer substrates is demonstrated as a capacitive humidity-sensing material. The bendable and porous SiO2/Si films are simply prepared by electrochemical-assisted stripping, metal-assisted chemical etching, followed by oxidation procedures. The capacitive humidity-sensing properties of the fabricated porous SiO2/Si film are characterized as a function of the relative humidity and frequency. The remarkable sensing performance is demonstrated in the wide RH range from 13.8 to 79.0%. The sensing behavior of the porous SiO2/Si film is studied by electrochemical impedance spectroscopy analysis. Additionally, the reliability of the porous SiO2/Si sensing material is confirmed by cyclic and long-term sensing tests.

Synthesis of Copper Telluride Thin Films by Electrodeposition and Their Electrical and Thermoelectric Properties.

Intermetallic copper telluride thin films, which are important in a number of electronics fields, were electrodeposited using a potentiostatic method in low-pH aqueous electrolyte baths with various ion-source concentrations, and the electrical properties of the formed films were investigated after exfoliation from the substrate. The films were electrochemically analyzed by cyclic voltammetry, while surface and cross-sectional morphologies, compositional ratios, and electrical properties were analyzed by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and Hall-effect experiments. The copper telluride thin films, which were synthesized at various potentials in each bath, exhibit different composition ratios and structures; consequently, they show a variety of electrical and thermoelectric properties, including different electrical conductivities, carrier concentrations, mobilities, and Seebeck coefficients. Among them, the thin film with a 1:1 Cu:Te ratio delivered the highest power factor due to carrier filtering at the interface between the two phases.

Study of Cu Electrochemical Polishing Mechanism With Observation of Water Acceptor Diffusion.

The salt-film and water acceptor mechanisms were generally accepted mechanisms for Cu electrochemical polishing (ECP) theory. These mechanisms of Cu ECP are still controversial for a long time. Conventional and new electrochemical analysis methods were used to investigate the mechanisms and behaviors of Cu electrochemical polishing. Two cases of Cu dissolution, with and without polishing, were classified by results of linear scan voltammetry (LSV) and scanning electron microscopy (SEM). The electrochemical impedance spectroscopy (EIS) results showed the main difference in these two cases was in the low-frequency region. However, it was hard to distinguish between the salt-film and water acceptor mechanisms by conventional electrochemical analysis. A scanning electrochemical microscopy (SECM) system, a new electrochemical analysis method that measures the electrolysis currents of the water acceptors along with a set distance from the substrate, was used to investigate the Cu ECP mechanism. Accordingly, the diffusion of the water acceptors was successfully confirmed for the first time. Finally, the mechanisms of the Cu ECP are definitively described by using all analysis results.

Metal-free high-adsorption-capacity adsorbent derived from spent coffee grounds for methylene blue.

Heavy-metal-free carbon materials were prepared from spent coffee grounds (SCG) using the coupled KOH-urea and NaOH-urea as activating agents, and these were compared with SCG activation by the alkali salts alone. SCG was impregnated with the activating agents before being pyrolyzed at 800 °C under a N2 atmosphere. Characterization of the as-pyrolyzed carbon materials was performed by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and measurement of N2 adsorption-desorption isotherms. The carbon materials were utilized for the adsorption of methylene blue (MB) in aqueous solutions. Combining KOH and urea as activating agents resulted in the generation of pertinent SCG-derived carbon material properties, including a large surface area (1665.45 m2 g-1) and excellent MB adsorption capacity. Adsorption efficiencies were studied using adsorption kinetics (pseudo-first-order and pseudo-second-order) and adsorption isotherm (Langmuir, Freundlich, and Temkin) models. The influences of pH and temperature were investigated. The results of this work raise new possibilities for synthesizing carbon materials with high MB adsorption capacities from biowastes, via less-toxic, energy-saving conventional pyrolysis methods for water-treatment applications.

Effect of Pulse Current and Pre-annealing on Thermal Extrusion of Cu in Through-Silicon via (TSV).

Thermal stress induced by annealing the Cu filling of through-silicon vias (TSVs) requires further investigation as it can inhibit the performance of semiconductor devices. This study reports the filling behavior of TSVs prepared using direct current and pulse current Cu electrodeposition with and without pre-annealing. The thermal extrusion of Cu inside the TSVs was studied by observing the extrusion behavior after annealing and the changes in grain orientation using scanning electron microscopy and electron backscatter diffraction. The bottom-up filling ratio achieved by the direct current approach decreased because the current was used both to fill the TSV and to grow bump defects on the top surface of the wafer. In contrast, pulse current electrodeposition yielded an improved TSV bottom-up filling ratio and no bump defects, which is attributable to strong suppression and thin diffusion layer. Moreover, Cu deposited with a pulse current exhibited lesser thermal extrusion, which was attributed to the formation of nanotwins and a change in the grain orientation from random to (101). Based on the results, thermal extrusion of the total area of the TSVs could be obtained by pulse current electrodeposition with pre-annealing.

Improved Chloride Ion Sensing Performance of Flexible Ag-NPs/AgCl Electrode Sensor Using Cu-BTC as an Effective Adsorption Layer.

We designed the flexible chloride ion selective sensor that directly monitors electrochemical reactions of chloride ions without using a reference electrode. A flexible polytetrafluoroethylene (PTFE) substrate was utilized to provide bendability to the fabricated sensor. As an ion selective material, Ag nanoparticles were employed on the MWCNTs loaded on the PTFE substrate. Enhanced adsorption property of the fabricated sensor toward the chloride ions was given by incorporation of hydrophilic copper benzene-1,3,5-tricarboxylate (Cu-BTC) with great flexibility and stability. Accordingly, compared to the bare sensor the sensing performance of the Cu-BTC treated Ag NPs/AgCl electrode sensor was improved by indicating the decrease in response and recovery time about 4 times. It elucidated that the Cu-BTC layer could work as an effective medium between the Ag-NPs surface and electrolyte containing chloride ions. As a result of contact angle measurement, the hydrophilicity much increased in the Cu-BTC treated sensor because the exposed surface of the sensor not treated by the Cu-BTC largely consisted of hydrophobic MWCNTs. Furthermore, the Cu-BTC layer could hold the electrolyte for effective adsorption of analytes with large specific surface area.

Sulfur-Enhanced Field-Effect Passivation using (NH4)2S Surface Treatment for Black Si Solar Cells.

We demonstrated surface passivation of a black Si-based solar cell using an (NH4)2S solution to mitigate surface recombination velocity. Incorporated S at the interface between atomic-layer-deposited Al2O3 and black Si by (NH4)2S solution treatment boosted the density of negative fixed charges, S-enhanced field-effect passivation. Furthermore, NH4OH generated during (NH4)2S solution treatment removed the defective Si phase at the black Si surface, the surface cleaning effect. The optimized (NH4)2S solution treatment significantly enhanced the internal quantum efficiency up to ∼17.2% in the short wavelength region, suggesting suppressed surface recombination. As a result, photoconversion efficiency of the cell increased from 11.6 to 13.5%, by 16% compared to the control cells without (NH4)2S solution treatment.

Electrochemical Polishing of Cu Redistribution Layers for Fan-Out Wafer Level Packaging.

Cu overburden layers on the trenches from redistribution layer process of fan-out wafer level packaging were successfully polished by electrochemical polishing method. For the uniform electrochemical polishing of Cu overburden on inside and outside of the trenches, thickness of the Cu overburden was controlled to have same thickness at the both side of trenches by addition of the additives such as accelerator, suppressor, and leveler. Before the electrochemical polishing of Cu overburden, optimum polishing potential and polishing rates were determined to 1.3 V and 462 nm/C · cm-2 through the cyclic voltammetry analysis and observation of electrochemical polishing behavior of Cu planar substrate in 85% H3PO4. Electrochemical polishing of Cu overburden was carried out at the condition determined from the previous experiment. The results of electrochemical polishing indicated that Cu overburden on both side of trenches was totally removed simultaneously at the end of electrochemical polishing and Cu overburden profile was important for the uniform planarization of Cu overburden on both side of the trenches.

Kerf-Less Exfoliated Thin Silicon Wafer Prepared by Nickel Electrodeposition for Solar Cells.

Ultra-thin and large-area silicon wafers with a thickness in the range of 20-70 µm, were produced by spalling using a nickel stressor layer. A new equation for predicting the thickness of the spalled silicon was derived from the Suo-Hutchinson mechanical model and the kinking mechanism. To confirm the reliability of the new equation, the proportional factor of stress induced by the nickel on the silicon wafer, was calculated. The calculated proportional factor of λ = 0.99 indicates that the thickness of the spalled silicon wafer is proportional to that of the nickel layer. A similar relationship was observed in the experimental data obtained in this study. In addition, the thickness of the stressor layer was converted to a value of stress as a guide when using other deposition conditions and materials. A silicon wafer with a predicted thickness of 50 µm was exfoliated for further analysis. In order to spall a large-area (150 × 150 mm2 or 6 × 6 in2) silicon wafer without kerf loss, initial cracks were formed by a laser pretreatment at a proper depth (50 µm) inside the exfoliated silicon wafer, which reduced the area of edge slope (kerf loss) from 33 to 3 mm2. The variations in thickness of the spalled wafer remained under 4%. Moreover, we checked the probability of degradation of the spalled wafers by using them to fabricate solar cells; the efficiency and ideality factor of the spalled silicon wafers were found to be 14.23%and 1.35, respectively.

Toward a planar black silicon technology for 50 µm-thin crystalline silicon solar cells.

Auger and surface recombinations are major drawbacks that deteriorate a photon-to-electron conversion efficiencies in nanostructured (NS) Si solar cells. As an alternative to conventional frontside nanostructuring, we report how backside nanostructuring is beneficial for carrier collection during photovoltaic operation that utilizes a 50-µm-thin wafer. Ultrathin (4.3-nm-thin) zinc oxide was also effective for providing passivated tunneling contacts at the nanostructured backsides, which led to the enhancement of 24% in power conversion efficiency.

Electrodeposition of Nanotwin Cu by Pulse Current for Through-Si-Via (TSV) Process.

Recently, the through-Si-via (TSV) had been focused as an optimal solution for interconnecting the 3-dimensionaly stacked semiconductor devices. One of core processes in the TSV technology is the Cu filling process which electrochemically forms the Cu in the via with high aspect ratio. The nanotwin Cu is effective candidate for replacing the conventional electrodeposited Cu due to its ultrahigh mechanical strength and good electrical conductivity. In this work, the formation of the nanotwin Cu in the TSV by applying pulse current was systematically studied. Also, TSV filling behavior by electrodeposition with pulse current was compared with direct current. The variation of mechanical properties as well as the electrical resistivity of electrodeposited Cu by the pulse current also investigated.

Microfabrication for Drug Delivery.

This review is devoted to discussing the application of microfabrication technologies to target challenges encountered in life processes by the development of drug delivery systems. Recently, microfabrication has been largely applied to solve health and pharmaceutical science issues. In particular, fabrication methods along with compatible materials have been successfully designed to produce multifunctional, highly effective drug delivery systems. Microfabrication offers unique tools that can tackle problems in this field, such as ease of mass production with high quality control and low cost, complexity of architecture design and a broad range of materials. Presented is an overview of silicon- and polymer-based fabrication methods that are key in the production of microfabricated drug delivery systems. Moreover, the efforts focused on studying the biocompatibility of materials used in microfabrication are analyzed. Finally, this review discusses representative ways microfabrication has been employed to develop systems delivering drugs through the transdermal and oral route, and to improve drug eluting implants. Additionally, microfabricated vaccine delivery systems are presented due to the great impact they can have in obtaining a cold chain-free vaccine, with long-term stability. Microfabrication will continue to offer new, alternative solutions for the development of smart, advanced drug delivery systems.

Morphological Transformation Reactions of Photocatalytic Metalloporphyrin-Containing Coordination Polymer Particles from Seed Structures.

Coordination polymer particles have attracted a great deal of attention due to their characteristic properties and diverse applications in the fields of gas storage, catalysis, optics, sensing, electronics, photochemistry, and biology. Herein, we investigated shape transformation reactions of zinc 5, 10, 15, 20-tetra(4-pyridyl)-21 H, 23 H-porphine (ZnTPyP)-containing coordination polymer particles (ZnTPyP-CPPs) from seed structures by delicately controlling the Gibbs energy of the self-assembly system. We obtained a morphological transformation from 1 D short nanorods to 1 D long nanorods and 3 D nano-octahedral structures, and from 3 D nano-octahedral structures to 1 D nanorod structures. We illustrated a new method to design and synthesize metalloporphyrin-containing CPPs in a controllable manner. Furthermore, photocatalytic properties of ZnTPyP-CPPs were tested, showing good catalytic abilities towards the photodegradation of methylene blue (MB) under visible light illumination.

Electrochemically decorated ZnTe nanodots on single-walled carbon nanotubes for room-temperature NO2 sensor application.

A gas sensor with ZnTe nanodot-modified single-walled carbon nanotubes (SWCNTs) is demonstrated for NO2 detection at room temperature. ZnTe nanodots are electrochemically deposited in an aqueous solution containing ZnSO4, TeO2 and citrate. A deposition potential range of ZnTe formation of -0.65 to -0.9 V is determined by cyclic voltammetry, and an intermetallic ZnTe compound is formed at above 50 degrees C bath. SWCNT-based sensors show the highly sensitive response down to 1 ppm NO2 gas at room temperature. In particular, the sensitivity of ZnTe nanodot-modified SWCNTs is increased by 6 times as compared to that of pristine SWCNT sensors. A selectivity test of SWCNT-ZnTe nanodots sensors is carried out with ammonia gas (NH3) and methanol vapor (MeOH), and the result confirms an excellent selectivity to NO2 gas.

Lossless hybridization between photovoltaic and thermoelectric devices.

The optimal hybridization of photovoltaic (PV) and thermoelectric (TE) devices has long been considered ideal for the efficient harnessing solar energy. Our hybrid approach uses full spectrum solar energy via lossless coupling between PV and TE devices while collecting waste energy from thermalization and transmission losses from PV devices. Achieving lossless coupling makes the power output from the hybrid device equal to the sum of the maximum power outputs produced separately from individual PV and TE devices. TE devices need to have low internal resistances enough to convey photo-generated currents without sacrificing the PV fill factor. Concomitantly, a large number of p-n legs are preferred to drive a high Seebeck voltage in TE. Our simple method of attaching a TE device to a PV device has greatly improved the conversion efficiency and power output of the PV device (~30% at a 15°C temperature gradient across a TE device).

Characterization and stability of liposome-enveloped trypsin/Fe3O4 for drug delivery and drug release behavior.

Liposome encapsulating Fe3O4 (liposome complexes) has been prepared for targeting a drug to a specific organ, as well as for MRI (magnetic resonance imaging) contrast agents. The objective of the present work was to investigate the Fe3O4 properties and the effects of chitosan concentration on the characteristics of chitosan-coated liposome complexes. They were characterized by DLS, FT-IR, XRD, VSM, UV-Vis spectrometer, TEM and phase-contrast microscopy. The average liposome complex size was approximately 500 nm, with individual Fe3O4 nanoparticle sizes of 10 nm. The drug incorporation efficiency of trypsin in liposome complexes was 65-69%, the drug release was sustained and the incorporated drugs had the magnetization properties of the liposome complexes. Incorporation of chitosan into the liposome bilayer decreased trypsin release from the liposome complexes due to an increased rigidity of the liposome membrane structure. Chitosan-coated liposome complexes showed a higher stability when compared with the stability of non-coated liposome complexes.

A glucose sensor fabricated by piezoelectric inkjet printing of conducting polymers and bienzymes.

Piezoelectric inkjet printing of polymers and proteins holds great promise for fabrication of miniaturized bioelectronic devices, such as biochips and biosensors. In this study, a bienzymatic glucose biosensor prototype based on poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS), glucose oxidase (GOD), and horseradish peroxidase (HRP) was fabricated by a piezoelectric inkjet printer. An aqueous bioelectrical ink containing PEDOT-PSS, GOD, and HRP was prepared and printed on an indium-tin-oxide (ITO)-coated poly(ethylene terephthalate) (PET) film. The PEDOT-PSS/GOD/HRP sensor was covered with a cellulose acetate membrane. The use of bienzymatic sensing combined with conducting polymers via piezoelectric inkjet printing showed a synergistic effect resulting in significant amplification of the response signal. The glucose sensor reached steady-state current density within 3 s, indicating a fast response time, and exhibited a linear dose-dependent electrochemical response with high sensitivity. The overall result demonstrates that a glucose sensor with high sensitivity could be readily fabricated by a piezoelectric inkjet printing system.

Peptide-mediated shape- and size-tunable synthesis of gold nanostructures.

While several biological processes have been shown to be useful for the production of well-designed, inorganic nanostructures, the mechanism(s) controlling the size and shape of nano and micron size particles remains elusive. Here we report on the controlled size- and shape-specific production of gold nanostructures under ambient reaction conditions using a dodecapeptide, Midas-2, originally selected from a phage-displayed combinatorial peptide library. Single amino acid changes in Midas-2 greatly influence the size (a few nanometers to approximately 100 microm) and shape (nanoparticles, nanoribbons, nanowires and nanoplatelets) of the gold nanostructures produced, and these are controllable by adjusting the solution pH and gold ion concentration. The ability to control the shape and size of the gold nanostructures by changing the peptide structure and reaction conditions will lead to many potential applications, including nanoelectronics, sensors and optoelectronics, because of their unique size- and shape-dependent optical and electrical properties.