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H-Si(111)-terminated surfaces were alkenylated via two routes: through a novel one-step gas-phase hydrosilylation reaction with short alkynes (C to C) and for comparison via a two-step chlorination and Grignard alkenylation process. All modified surfaces were characterized by static water contact angles and X-ray photoelectron spectroscopy (XPS). Propenyl- and butenyl-coated Si(111) surfaces display a significantly higher packing density than conventional C-C alkyne-derived monolayers, showing the potential of this approach. In addition, propyne chemisorption proceeds via either of two approaches: the standard hydrosilylation at the terminal carbon (lin) at temperatures above 90 °C and an unprecedented reaction at the second carbon (iso) at temperatures below 90 °C. Molecular modeling revealed that the packing energy of a monolayer bonded at the second carbon is significantly more favorable, which drives iso-attachment, with a dense packing of surface-bound iso-propenyl chains at 40% surface coverage, in line with the experiments at <90 °C. The highest density monolayers are obtained at 130 °C and show a linear attachment of 1-propenyl chains with 92% surface coverage.
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http://dx.doi.org/10.1021/acs.langmuir.7b03683 | DOI Listing |
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July 2025
Department of Chemistry and Center for Emerging Materials and Advanced Devices, National Taiwan University, Taipei, 106319, Taiwan ROC.
Tantalum nitride (TaN) shows promising prospects for photoelectrochemical (PEC) water splitting due to its suitable band gap and band edge positions. However, high-performing TaN photoanodes typically require Ta foil substrates and film thicknesses of several hundred nanometers, leading to increased tantalum usage and fabrication costs. This study introduces bixbyite-type TaN as a superior precursor for synthesizing thin (≈100 nm) TaN films on silicon substrates, substantially reducing tantalum consumption while maintaining excellent PEC performance.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements.
View Article and Find Full Text PDFNanotechnology
April 2025
School of Materials Science, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa 923-1292, Japan.
Silicon (Si) (111)-(7 × 7) surfaces with wide terraces and bunched steps were passivated with atomic hydrogen (H) and subsequently etched by irradiation of atomic H. The atomic H can suppress the reactivity of Si surfaces by terminating the dangling bonds of Si surfaces. Meanwhile, atomic H can break the periodic atomic structures such as (7 × 7) on the Si surfaces.
View Article and Find Full Text PDFJ Phys Chem Lett
March 2025
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58102, United States.
The efficiency of silicon solar cells is affected by the light absorption and recombination losses of photoexcited charge carries. One possible way to improve the efficiency is through the deposition of transition metal nanoparticles on Si surfaces. Here, we first carry out density functional theory (DFT) calculations to obtain electronic structures for Ag ( = 1-7) monolayered clusters adsorbed on Si(111)/H surfaces.
View Article and Find Full Text PDFSci Rep
March 2025
Department of Engineering Science, The University of Electro-Communications (UEC Tokyo), Chofu, Tokyo, 182-8585, Japan.
A method to simulate the dipole moment mode of the scanning nonlinear dielectric microscope (SNDM) has been developed. This method has been applied to the so-called [Formula: see text] dimer-adatom-stacking-fault (DAS) structure and a [Formula: see text] surface with one adatom and one restatom, which are the main motifs of the DAS structure. It has been revealed that a local upward dipole moment is observed at the adatom site, consistent with the SNDM experiments.
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