Stress Relaxation and Grain Growth Behaviors of (111)-Preferred Nanotwinned Copper during Annealing.

Highly (111)-oriented nanotwinned Cu (nt-Cu) films were fabricated on silicon wafers for thermal-stress characterization. We tailored the microstructural features (grain scale and orientation) of the films by tuning the electroplating parameters. The films were heat-treated and the relaxation behaviors of thermal stresses in the films were explored using a bending beam system. Focused ion beam (FIB) and electron back-scattered diffraction (EBSD) were then employed to characterize the transformations of the microstructure, grain size, and orientation degree of the films. The results indicated that the degree of (111)-preferred orientation and grain size significantly decrease with increasing the current density. The nt-Cu films with a higher degree of (111)-preferred orientation and larger grains exhibit the slower rates of stress relaxation. The film with larger grains possesses a smaller grain boundary area; thus, the grain boundary diffusion for the thermal-stress release is suppressed. In addition, the induced tensile stress in the films with larger grains is smaller leading to the difference in microstructural changes under annealing.

Pentafluoropyridine functionalized novel heteroatom-doped with hierarchical porous 3D cross-linked graphene for supercapacitor applications.

The fabrication with high energy density and superior electrical/electrochemical properties of hierarchical porous 3D cross-linked graphene-based supercapacitors is one of the most urgent challenges for developing high-power energy supplies. We facilely synthesized a simple, eco-friendly, cost-effective heteroatoms (nitrogen, phosphorus, and fluorine) co-doped graphene oxide (NPFG) reduced by hydrothermal functionalization and freeze-drying approach with high specific surface areas and hierarchical pore structures. The effect of different heteroatoms doping on the energy storage performance of the synthesized reduced graphene oxide is investigated extensively. The electrochemical analysis performed in a three-electrode system via cyclic voltammetry (CV), galvanostatic charging-discharging (GCD), and electrochemical impedance spectroscopy (EIS) demonstrates that the nitrogen, phosphorous, and fluorine co-doped graphene (NPFG-0.3) synthesized with the optimum amount of pentafluoropyridine and phytic acid (PA) exhibits a notably enhanced specific capacitance (319 F g-1 at 0.5 A g-1), good rate capability, short relaxation time constant (τ = 28.4 ms), and higher diffusion coefficient of electrolytic cations (Dk+ = 8.8261 × 10-9 cm2 s-1) in 6 M KOH aqueous electrolyte. The density functional theory (DFT) calculation result indicates that the N, F, and P atomic replacement within the rGO model could increase the energy value (G T) from -673.79 eV to -643.26 eV, demonstrating how the atomic level energy could improve the electrochemical reactivity with the electrolyte. The improved performance of NPFG-0.3 over NFG, PG, and pure rGO is mainly ascribed to the fast-kinetic process owing to the well-balanced electron/ion transport phenomenon. A symmetric coin cell supercapacitor device fabricated using NPFG-0.3 as the anode and cathode material with 6 M KOH aqueous electrolyte exhibits maximum specific energy of 38 W h kg-1, a maximum specific power of 716 W kg-1, and ∼88.2% capacitance retention after 10 000 cycles. The facile synthesis approach and promising electrochemical results suggest this synthesized NPFG-0.3 material has high potential for future supercapacitor application.

Effects of Methyl Terminal and Carbon Bridging Groups Ratio on Critical Properties of Porous Organosilicate-Glass Films.

Organosilicate glass-based porous low dielectic constant films with different ratios of terminal methyl to bridging organic (methylene, ethylene and 1,4-phenylene) groups are spin-on deposited by using a mixture of alkylenesiloxane with organic bridges and methyltrimethoxysilane, followed by soft baking at 120-200 °C and curing at 430 °C. The films' porosity was controlled by using sacrificial template Brij® L4. Changes of the films' refractive indices, mechanical properties, k-values, porosity and pore structure versus chemical composition of the film's matrix are evaluated and compared with methyl-terminated low-k materials. The chemical resistance of the films to annealing in oxygen-containing atmosphere is evaluated by using density functional theory (DFT). It is found that the introduction of bridging groups changes their porosity and pore structure, increases Young's modulus, but the improvement of mechanical properties happens simultaneously with the increase in the refractive index and k-value. The 1,4-phenylene bridging groups have the strongest impact on the films' properties. Mechanisms of oxidative degradation of carbon bridges are studied and it is shown that 1,4-phenylene-bridged films have the highest stability. Methylene- and ethylene-bridged films are less stable but methylene-bridged films show slightly higher stability than ethylene-bridged films.

Synthesis of Free-Standing Flexible rGO/MWCNT Films for Symmetric Supercapacitor Application.

Herein, we report a novel, simple, and cost-effective way to synthesize flexible and conductive rGO and rGO/MWCNT freestanding films. The effects of MWCNT addition on the electrochemical performance of rGO/MWCNT nanocomposite films are investigated in some strong base aqueous electrolytes, such as KOH, LiOH, and NaOH via three-electrode system. The supercapacitor behavior of the films is probed via cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy. The structural and morphological studies of the films are performed by X-ray diffractometer, Raman spectrometer, surface area analyzer, thermogravimetric analysis, field emission scanning electron microscope and transmission electron microscope. The rGO/MWCNT film synthesized with 10 wt% MWCNTs (GP10C) exhibits high specific capacitance of 200 Fg-1, excellent cyclic stability with 92% retention after 15,000 long cycle test, small relaxation time constant (~ 194 ms), and high diffusion coefficient (7.8457 × 10-9 cm2 s-1) in 2 M KOH electrolyte. Furthermore, the symmetric supercapacitor coin cell with GP10C as both anode and cathode using 2 M KOH as electrolyte demonstrates high energy density of 29.4 Whkg-1 and power density of 439 Wkg-1 at current density 0.1 Ag-1 and good cyclic stability with 85% retention of the initial capacitance at 0.3 Ag-1 after 10,000 cycles. Such a high performance of the GP10C film in the supercapacitor can be ascribed to the large surface area and small hydration sphere radius and high ionic conductivity of K+ cations in KOH electrolyte.

Enhanced Photocatalytic Performance of Nitrogen-Doped TiO2 Nanotube Arrays Using a Simple Annealing Process.

Nitrogen-doped TiO2 nanotube arrays (N-TNAs) were successfully fabricated by a simple thermal annealing process in ambient N2 gas at 450 °C for 3 h. TNAs with modified morphologies were prepared by a two-step anodization using an aqueous NH4F/ethylene glycol solution. The N-doping concentration (0⁻9.47 at %) can be varied by controlling N2 gas flow rates between 0 and 500 cc/min during the annealing process. Photocatalytic performance of as-prepared TNAs and N-TNAs was studied by monitoring the methylene blue degradation under visible light (λ ≥ 400 nm) illumination at 120 mW·cm-2. N-TNAs exhibited appreciably enhanced photocatalytic activity as compared to TNAs. The reaction rate constant for N-TNAs (9.47 at % N) reached 0.26 h-1, which was a 125% improvement over that of TNAs (0.115 h-1). The significant enhanced photocatalytic activity of N-TNAs over TNAs is attributed to the synergistic effects of (1) a reduced band gap associated with the introduction of N-doping states to serve as carrier reservoir, and (2) a reduced electron‒hole recombination rate.

Anisotropic optical transmission of femtosecond laser induced periodic surface nanostructures on indium-tin-oxide films.

Two types of periodic nanostructures, self-organized nanodots and nanolines, were fabricated on the surfaces of indium-tin-oxide (ITO) films using femtosecond laser pulse irradiation. Multiple periodicities (approximately 800 nm and 400 nm) were clearly observed on the ITO films with nanodot and nanoline structures and were identified using two-dimensional Fourier transformation patterns. Both nanostructures show the anisotropic transmission characteristics in the visible range, which are strongly correlated with the geometry and the metallic content of the laser-induced nanostructures.

Superior local conductivity in self-organized nanodots on indium-tin-oxide films induced by femtosecond laser pulses.

Large-area surface ripple structures of indium-tin-oxide films, composed of self-organized nanodots, were induced by femtosecond laser pulses, without scanning. The multi-periodic spacing (~800 nm, ~400 nm and ~200 nm) was observed in the laser-induced ripple of ITO films. The local conductivity of ITO films is significantly higher, by approximately 30 times, than that of the as-deposited ITO films, due to the formation of these nanodots. Such a significant change can be ascribed to the formation of indium metal-like clusters, which appear as budges of ~5 nm height, due to an effective volume increase after breaking the In-O to form In-In bonding.