Jiheng Zhao

Enabling silicon photoanodes for efficient solar water splitting by electroless-deposited nickel

Enabling Si photoanodes for efficient solar water oxidation would facilitate the development of solar fuel conversion, but it is challenging owing to Si surface passivation via photo-induced corrosion in aqueous electrolytes. To overcome this challenge, most approaches have focused on improving the stability of Si by coating dense and thin protective layers using high vacuum-based techniques such as atomic layer deposition. However, these procedures are costly, making scalability for practical applications difficult. Herein, we report a modified electroless deposition (ELD) method to uniformly deposit protective and catalytic Ni films on Si wafers, resulting in efficient and stable Si photoanodes for solar water oxidation. The optimized Ni/n-Si photoanode achieves an onset potential of ∼ 1.09 V vs. a reversible hydrogen electrode and a saturation current density of ∼ 27.5 mA/cm2 under AM 1.5 G illumination at pH 14. The ELD method is additionally capable of Ni deposition on a 4-inch n-Si wafer, demonstrating the first 4-inch Si photoanode. The solar water oxidation of the ELD-Ni/n-Si photoanode can be further improved by surface texturing, built-in n–p junctions, or coupling with more efficient catalysts.

Electroless Deposition and Ignition Properties of Si/Fe2O3 Core/Shell Nanothermites

Thermite, a composite of metal and metal oxide, finds wide applications in power and thermal generation systems that require high-energy density. Most of the researches on thermites have focused on using aluminum (Al) particles as the fuel. However, Al particles are sensitive to electrostatic discharge, friction, and mechanical impact, imposing a challenge for the safe handling and storage of Al-based thermites. Silicon (Si) is another attractive fuel for thermites because of its high-energy content, thin native oxide layer, and facile surface functionality. Several studies showed that the combustion properties of Si-based thermites are comparable to those of Al-based thermites. However, little is known about the ignition properties of Si-based thermites. In this work, we determined the reaction onset temperatures of mechanically mixed (MM) Si/Fe2O3 nanothermites and Si/Fe2O3 core/shell (CS) nanothermites using differential scanning calorimetry. The Si/Fe2O3 CS nanothermites were prepared by an electroless deposition method. We found that the Si/Fe2O3 CS nanoparticles (NPs) had a lower reaction onset temperature (∼550 °C) than the MM Si/Fe2O3 nanothermites (>650 °C). The onset temperature of the Si/Fe2O3 CS nanothermites is also insensitive to the size of the Si core NP. These results indicate that the interfacial contact quality between Si and Fe2O3 is the dominant factor for determining the ignition properties of thermites. Finally, the reaction onset temperature of the Si/Fe2O3 CS NPs is comparable to that of the commonly used Al-based nanothermites, suggesting that Si is an attractive fuel for thermites.

Molybdenum disulfide catalyzed tungsten oxide for on-chip acetone sensing

Acetone sensing is critical for acetone leak detection and holds a great promise for the noninvasive diagnosis of diabetes. It is thus highly desirable to develop a wearable acetone sensor that has low cost, miniature size, sub-ppm detection limit, great selectivity, as well as low operating temperature. In this work, we demonstrate a cost-effective on-chip acetone sensor with excellent sensing performances at 200 °C using molybdenum disulfide (MoS2) catalyzed tungsten oxide (WO3). The WO3 based acetone sensors are first optimized via combined mesoscopic nanostructuring and silicon doping. Under the same testing conditions, our optimized mesoporous silicon doped WO3 [Si:WO3(meso)] sensor shows 2.5 times better sensitivity with ∼1000 times smaller active device area than the state-of-art WO3 based acetone sensor. Next, MoS2 is introduced to catalyze the acetone sensing reactions for Si:WO3(meso), which reduces the operating temperature by 100 °C while retaining its high sensing performances. Our miniaturiz...

Epitaxial growth of WO3 nanoneedles achieved using a facile flame surface treatment process engineering of hole transport and water oxidation reactivity

Charge carrier dynamics and light harvesting abilities are of the most important roles to the performance of a photoanode in the Photoelectrochemical (PEC) area. In this work, through a facile flame surface treatment process in a reducing atmosphere, oriented WO3 nanoneedles are grown on pre-formed vertically aligned nanohelices. Nanohelices have excellent light harvesting abilities on their own, however, the addition of nanoneedles to the top of nanohelices increases the light harvesting abilities even further. More importantly, the reducing atmosphere for the post treatment process enhances the metallic property of WO3, changes the band position to facilitate hole transport, and modifies the flat band potential, all of which contribute to an improved performance regarding the photocurrent density and onset. The as fabricated nanohelices/nanoneedles WO3 with metallic interface has also been used for heterojunction photoanode fabrication for water oxidation through two- and four- electron pathways for H2O2 and O2 production, respectively.Charge carrier dynamics and light harvesting ability are most important for the performance of a photoanode in photoelectrochemical (PEC) systems. In this work, through a facile flame surface treatment process in a reducing atmosphere, oriented WO3 nanoneedles are grown on pre-formed vertically aligned nanohelices. Nanohelices have excellent light harvesting abilities on their own; however, the addition of nanoneedles to the top of nanohelices increases the light harvesting abilities even further. More importantly, the reducing atmosphere for the post-treatment process enhances the metallic properties of WO3, changes the band position to facilitate hole transport, and modifies the flat band potential, all of which contribute to an improved performance in terms of photocurrent density and onset. The as-fabricated WO3 nanohelices/nanoneedles with a metallic interface have also been used for heterojunction photoanode fabrication for water oxidation through two- and four-electron pathways for H2O2 and O2 production, respectively.

Energetic Performance of Optically Activated Aluminum/Graphene Oxide Composites

Optical ignition of solid energetic materials, which can rapidly release heat, gas, and thrust, is still challenging due to the limited light absorption and high ignition energy of typical energetic materials ( e.g., aluminum, Al). Here, we demonstrated that the optical ignition and combustion properties of micron-sized Al particles were greatly enhanced by adding only 20 wt % of graphene oxide (GO). These enhancements are attributed to the optically activated disproportionation and oxidation reactions of GO, which release heat to initiate the oxidization of Al by air and generate gaseous products to reduce the agglomeration of the composites and promote the pressure rise during combustion. More importantly, compared to conventional additives such as metal oxides nanoparticles ( e.g., WO3 and Bi2O3), GO has much lower density and therefore could improve energetic properties without sacrificing Al content. The results from Xe flash ignition and laser-based excitation experiments demonstrate that GO is an efficient additive to improve the energetic performance of micron-sized Al particles, enabling micron-sized Al to be ignited by optical activation and promoting the combustion of Al in air.

Conformal Electroless Nickel Plating on Silicon Wafers, Convex and Concave Pyramids, and Ultralong Nanowires

Nickel (Ni) plating has garnered great commercial interest, as it provides excellent hardness, corrosion resistance, and electrical conductivity. Though Ni plating on conducting substrates is commonly employed via electrodeposition, plating on semiconductors and insulators often necessitates electroless approaches. Corresponding plating theory for deposition on planar substrates was developed as early as 1946, but for substrates with micro- and nanoscale features, very little is known of the relationships between plating conditions, Ni deposition quality, and substrate morphology. Herein, we describe the general theory and mechanisms of electroless Ni deposition on semiconducting silicon (Si) substrates, detailing plating bath failures and establishing relationships between critical plating bath parameters and the deposited Ni film quality. Through this theory, we develop two different plating recipes: galvanic displacement (GD) and autocatalytic deposition (ACD). Neither recipe requires pretreatment of the Si substrate, and both methods are capable of depositing uniform Ni films on planar Si substrates and convex Si pyramids. In comparison, ACD has better tunability than GD, and it provides a more conformal Ni coating on complex and high-aspect-ratio Si structures, such as inverse fractal Si pyramids and ultralong Si nanowires. Our methodology and theoretical analyses can be leveraged to develop electroless plating processes for other metals and metal alloys and to generally provide direction for the adaptation of electroless deposition to modern applications.