In Situ Monitoring of the Polymerization Kinetics of Organic Pollutants during Persulfate-Based Advanced Oxidation Processes Using Plasmonic Colorimetry.

Using sulfate radicals to initiate polymer production in persulfate-based advanced oxidation processes (AOPs) is an emerging strategy for organics removal. However, our understanding of this process remains limited due to a dearth of efficient methods for in situ and real time monitoring of polymerization kinetics. This study leverages plasmonic colorimetry to monitor the polymerization kinetics of an array of aromatic pollutants in the presence of sulfate radicals. We observed that the formation of polymer shells on the surfaces of gold nanoparticles (AuNPs) led to an increase and red shift in their localized surface plasmon resonance (LSPR) band as a result of an increased refractive index surrounding the AuNP surfaces. This observation aligns with Mie theory simulations and transmission electron microscopy-electron energy loss spectroscopy characterizations. Our study demonstrated that the polymerization kinetics exhibits a significant reliance on the electrophilicity and quantity of benzene rings, the concentration of aromatic pollutants, and the dosage of oxidants. In addition, we found that changes in LSPR band wavelength fit well into a pseudo-first-order kinetic model, providing a comprehensive and quantitative insight into the polymerization kinetics involving diverse organic compounds. This technique holds the potential for optimizing AOP-based water treatment by facilitating the polymerization of aromatic pollutants.

Optimizing Nonrigid Registration for Scanning Transmission Electron Microscopy Image Series.

Achieving sub-picometer precision measurements of atomic column positions in high-resolution scanning transmission electron microscope images using nonrigid registration (NRR) and averaging of image series requires careful optimization of experimental conditions and the parameters of the registration algorithm. On experimental data from SrTiO3 [100], sub-pm precision requires alignment of the sample to the zone axis to within 1 mrad tilt and sample drift of less than 1 nm/min. At fixed total electron dose for the series, precision in the fast scan direction improves with shorter pixel dwell time to the limit of our microscope hardware, but the best precision along the slow scan direction occurs at 6 µs/px dwell time. Within the NRR algorithm, the "smoothness factor" that penalizes large estimated shifts is the most important parameter for sub-pm precision, but in general, the precision of NRR images is robust over a wide range of parameters.

High Aspect Ratio ß-Ga2O3 Fin Arrays with Low-Interface Charge Density by Inverse Metal-Assisted Chemical Etching.

ß-Ga2O3, with a bandgap of ∼4.6-4.9 eV and readily available bulk substrates, has attracted tremendous interest in the wide bandgap semiconductor community. Producing high aspect ratio ß-Ga2O3 3D nanostructures without surface damage is crucial for next-generation power electronics. However, most wet etching methods can only achieve very limited aspect ratios, while dry etch usually damages the surface due to high energy ions. In this work, we demonstrate the formation of ß-Ga2O3 fin arrays on a (010) ß-Ga2O3 substrate by metal-assisted chemical etching (MacEtch) with high aspect ratio and sidewall surfaces with excellent quality. The etching was found to be strongly crystal orientation dependent, and three kinds of vertical structures were formed after MacEtch. The Schottky barrier height (SBH) between Pt and various MacEtch-produced ß-Ga2O3 surfaces and sidewalls was found to decrease as the aspect ratio of the ß-Ga2O3 vertical structure increased. This could be attributed to the different amount of oxygen lost at the surface after etching, as indicated by the XPS and TEM examination. Very little hysteresis was observed in the capacitance-voltage characteristics for the 3D Pt/Al2O3/ß-Ga2O3 MOS capacitor structures, and the extracted interface trap density was as small as 2.73 × 1011 cm-2 eV-1, comparable to or lower than that for unetched planar ß-Ga2O3 surfaces.

Enhanced Performance of Ge Photodiodes via Monolithic Antireflection Texturing and α-Ge Self-Passivation by Inverse Metal-Assisted Chemical Etching.

Surface antireflection micro and nanostructures, normally formed by conventional reactive ion etching, offer advantages in photovoltaic and optoelectronic applications, including wider spectral wavelength ranges and acceptance angles. One challenge in incorporating these structures into devices is that optimal optical properties do not always translate into electrical performance due to surface damage, which significantly increases surface recombination. Here, we present a simple approach for fabricating antireflection structures, with self-passivated amorphous Ge (α-Ge) surfaces, on single crystalline Ge (c-Ge) surface using the inverse metal-assisted chemical etching technology (I-MacEtch). Vertical Schottky Ge photodiodes fabricated with surface structures involving arrays of pyramids or periodic nano-indentations show clear improvements not only in responsivity, due to enhanced optical absorption, but also in dark current. The dark current reduction is attributed to the Schottky barrier height increase and self-passivation effect of the i-MacEtch induced α-Ge layer formed on top of the c-Ge surface. The results demonstrated in this work show that MacEtch can be a viable technology for advanced light trapping and surface engineering in Ge and other semiconductor based optoelectronic devices.

Ferroelectric Polarization-Enhanced Photoelectrochemical Water Splitting in TiO2-BaTiO3 Core-Shell Nanowire Photoanodes.

The performances of heterojunction-based electronic devices are extremely sensitive to the interfacial electronic band structure. Here we report a largely enhanced performance of photoelectrochemical (PEC) photoanodes by ferroelectric polarization-endowed band engineering on the basis of TiO2/BaTiO3 core/shell nanowires (NWs). Through a one-step hydrothermal process, a uniform, epitaxial, and spontaneously poled barium titanate (BTO) layer was created on single crystalline TiO2 NWs. Compared to pristine TiO2 NWs, the 5 nm BTO-coated TiO2 NWs achieved 67% photocurrent density enhancement. By numerically calculating the potential distribution across the TiO2/BTO/electrolyte heterojunction and systematically investigating the light absorption, charge injection and separation properties of TiO2 and TiO2/BTO NWs, the PEC performance gain was proved to be a result of the increased charge separation efficiency induced by the ferroelectric polarization of the BTO shell. The ferroelectric polarization could be switched by external electric field poling and yielded PEC performance gain or loss based on the direction of the polarization. This study evidence that the piezotronic effect (ferroelectric or piezoelectric potential-induced band structure engineering) holds great promises in improving the performance of PEC photoelectrodes in addition to chemistry and structure optimization.

Evolution of hollow TiO2 nanostructures via the Kirkendall effect driven by cation exchange with enhanced photoelectrochemical performance.

Hollow nanostructures are promising building blocks for electrode scaffolds and catalyst carriers in energy-related systems. In this paper, we report a discovery of hollow TiO2 nanostructure evolution in a vapor-solid deposition system. By introducing TiCl4 vapor pulses to ZnO nanowire templates, we obtained TiO2 tubular nanostructures with well-preserved dimensions and morphology. This process involved the cation exchange reaction between TiCl4 vapor and ZnO solid and the diffusion of reactants and products in their vapor or solid phases, which was likely a manifestation of the Kirkendall effect. The characteristic morphologies and the evolution phenomena of the hollow nanostructures from this vapor-solid system were in a good agreement with the Kirkendall effect discovered in solution systems. Complex hollow TiO2 nanostructures were successfully acquired by replicating various ZnO nanomorphologies, suggesting that this unique cation exchange process could also be a versatile tool for nanostructure replication in vapor-solid growth systems. The evolution of TiO2 nanotubes from ZnO NW scaffolds was seamlessly integrated with TiO2 NR branch growth and thus realized a pure TiO2-phased 3D NW architecture. Because of the significantly enlarged surface area and the trace amount of Zn left in the TiO2 crystals, such 3D TiO2 nanoforests demonstrated enhanced photoelectrochemical performance particularly under AM (air mass) 1.5G illumination, offering a new route for hierarchical functional nanomaterial assembly and application.

Thickness variations and absence of lateral compositional fluctuations in aberration-corrected STEM images of InGaN LED active regions at low dose.

Aberration-corrected scanning transmission electron microscopy images of the In(0.15)Ga(0.85)N active region of a blue light-emitting diode, acquired at ~0.1% of the electron dose known to cause electron beam damage, show no lateral compositional fluctuations, but do exhibit one to four atomic plane steps in the active layer's upper boundary. The area imaged was measured to be 2.9 nm thick using position averaged convergent beam electron diffraction, ensuring the sample was thin enough to capture compositional variation if it was present. A focused ion beam prepared sample with a very large thin area provides the possibility to directly observe large fluctuations in the active layer thickness that constrict the active layer at an average lateral length scale of 430 nm.

Cl-doped ZnO nanowires with metallic conductivity and their application for high-performance photoelectrochemical electrodes.

Doping semiconductor nanowires (NWs) for altering their electrical and optical properties is a critical strategy for tailoring the performance of nanodevices. ZnO NWs grown by hydrothermal method are pervasively used in optoelectronic, photovoltaic, and piezoelectric energy-harvesting devices. We synthesized in situ Cl-doped ZnO NWs with metallic conductivity that would fit seamlessly with these devices and improve their performance. Possible Cl doping mechanisms were discussed. UV-visible absorption spectroscopy confirmed the visible light transparency of Cl-doped ZnO NWs. Cl-doped ZnO NW/TiO2 core/shell-structured photoelectrochemical (PEC) anode was fabricated to demonstrate the application potential of highly conductive ZnO NWs. Higher photocurrent density and overall PEC efficiency compared with the undoped ZnO NW-based device were achieved. The successful doping and low resistivity of ZnO could unlock the potential of ZnO NWs for applications in low-cost flexible transparent electrodes.

Electron microscopy observation of TiO2 nanocrystal evolution in high-temperature atomic layer deposition.

Understanding the evolution of amorphous and crystalline phases during atomic layer deposition (ALD) is essential for creating high quality dielectrics, multifunctional films/coatings, and predictable surface functionalization. Through comprehensive atomistic electron microscopy study of ALD TiO2 nanostructures at designed growth cycles, we revealed the transformation process and sequence of atom arrangement during TiO2 ALD growth. Evolution of TiO2 nanostructures in ALD was found following a path from amorphous layers to amorphous particles to metastable crystallites and ultimately to stable crystalline forms. Such a phase evolution is a manifestation of the Ostwald-Lussac Law, which governs the advent sequence and amount ratio of different phases in high-temperature TiO2 ALD nanostructures. The amorphous-crystalline mixture also enables a unique anisotropic crystal growth behavior at high temperature forming TiO2 nanorods via the principle of vapor-phase oriented attachment.

Chemical vapor deposition of aluminum nanowires on metal substrates for electrical energy storage applications.

Metal nanowires show promise in a broad range of applications, but many synthesis techniques require complex methodologies. We have developed a method for depositing patterned aluminum nanowires (Al NWs) onto Cu, Ni, and stainless steel substrates using low-pressure decomposition of trimethylamine alane complex. The NWs exhibited an average diameter in the range from 45 to 85 nm, were crystalline, and did not contain a detectable amount of carbon impurities. Atomic layer deposition of 50 nm of vanadium oxide on the surface of Al NW allows fabrication of supercapacitor electrodes with volumetric capacitance in excess of 1400 F·cc(-3), which exceeds the capacitance of traditional activated carbon supercapacitor electrodes by more than an order of magnitude.

Tailoring the pore alignment for rapid ion transport in microporous carbons.

The power density and charge-discharge time of electrical double layer capacitors are largely determined by how fast the electrolyte ions can travel within the carbon electrode particles. Our systematic studies using zeolite-templated carbons show that an enhancement in ion transport rate by more than 2 orders of magnitude is possible by minimizing the micropore tortuosity. Very uniform carbon deposition was achieved using a well-controlled process involving the decomposition of acetylene precursor at a reduced pressure of 10 Torr and under a constant flow rate of 100 sccm. Selected carbon samples with well-aligned, straight micropores demonstrate high specific capacitance of up to 300 F/g and outstanding frequency response of up to 10 Hz for 250 microm thick electrodes, indicating an attractive combination of high specific energy and high specific power in electrical double layer capacitors. Such properties are critical for many peak-power hungry applications, such as the leveling of subsecond disturbances in power lines. Our findings provide guidance for the optimal design of porous carbons with greatly improved power storage characteristics.

High-rate electrochemical capacitors based on ordered mesoporous silicon carbide-derived carbon.

Microporous carbons, produced by selective etching of metal carbides in a chlorine-containing environment, offer narrow distribution of micropores and one of the highest specific capacitances reported when used in electrical double layer capacitors (EDLC) with organic electrolytes. Previously, the small micropores in these carbons served as an impediment to ion transport and limited the power storage characteristics of EDLC. Here we demonstrate, for the first time, how the preparation and application of templated carbide-derived carbon (CDC) can overcome the present limitations and show the route for dramatic performance enhancement. The ordered mesoporous channels in the produced CDC serve as ion-highways and allow for very fast ionic transport into the bulk of the CDC particles. The enhanced transport led to 85% capacitance retention at current densities up to approximately 20 A/g. The ordered mesopores in silicon carbide precursor also allow the produced CDC to exhibit a specific surface area up to 2430 m(2)/g and a specific capacitance up to 170 F/g when tested in 1 M tetraethylammonium tetrafluoroborate solution in acetonitrile, nearly doubling the previously reported values.

Dislocation-driven nanowire growth and Eshelby twist.

Hierarchical nanostructures of lead sulfide nanowires resembling pine trees were synthesized by chemical vapor deposition. Structural characterization revealed a screwlike dislocation in the nanowire trunks with helically rotating epitaxial branch nanowires. It is suggested that the screw component of an axial dislocation provides the self-perpetuating steps to enable one-dimensional crystal growth, in contrast to mechanisms that require metal catalysts. The rotating trunks and branches are the consequence of the Eshelby twist of screw dislocations with a dislocation Burgers vector along the 110 directions having an estimated magnitude of 6 +/- 2 angstroms for the screw component. The results confirm the Eshelby theory of dislocations, and the proposed nanowire growth mechanism could be general to many materials.