Fangyuan Tian

–NH– Termination of the Si(111) Surface by Wet Chemistry

For over a quarter of a century the hydrogen-terminated Si(111) single-crystalline surface has been the gold standard as a starting point for silicon surface modification chemistry. However, creating a well-defined and stable interface based on Si-N bonds has remained elusive. Despite the fact that azides, nitro compounds, and amines do lead to the formation of surface Si-N, each of these modification schemes produces additional carbon- or oxygen-containing functional groups that in turn react with the surface itself, leaving contaminants that affect the interface properties for any further modification protocols. We describe the preparation of a Si(111) surface functionalized predominantly with Si-NH-Si species based on chlorination followed by the room temperature ammonia treatment utilizing NH(3)-saturated tetrahydrofuran (THF). The obtained surface has been characterized by infrared spectroscopy and X-ray photoelectron spectroscopy. This analysis was supplemented with DFT calculations. This newly characterized surface will join the previously established H-Si(111) and Cl-Si(111) surfaces as a general starting point for the preparation of oxygen- and carbon-free interfaces, with numerous potential applications.

Silicon Surface Functionalization Targeting Si–N Linkages

Silicon substrates have been a fascinating topic of fundamental and applied research for well over 50 years. They have attracted even more attention over the last couple of decades with advances in chemical functionalization that made oxide-free silicon surfaces a reality. Fundamentally new electronic properties and chemical reactivity became available, and the focus of chemical research turned more toward targeting specific chemical bonds and functionalities on silicon. Although thermodynamics clearly drives most processes under ambient conditions toward the formation of an oxide layer, kinetic control of the oxidation processes and thermodynamic tricks based on gaining stability of surface monolayers with high-density assembly have allowed for the formation of stable Si-C bonds and Si-O-C linkages on oxide-free silicon crystals. This feature article targets recent advances in making Si-N linkages on the same oxide-free single crystals. It covers the range of chemical approaches to achieving this goal and offers possible chemistry that can take advantage of the systems produced. The present status of the field and the future directions of its development will be considered.

Monitoring N3 Dye Adsorption and Desorption on TiO2 Surfaces: A Combined QCM-D and XPS Study

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Low-Temperature Adsorption and Diffusion of Methanol in ZIF-8 Nanoparticle Films

The adsorption of methanol by a zeolitic imidazolate framework-8 (ZIF-8) nanoparticle thin film was studied in situ using temperature-programmed desorption and X-ray photoelectron spectroscopy under low-temperature, low-pressure conditions. Partial pore penetration was observed at 90 K, but upon increasing the exposure temperature of the film to 130 K pore penetration was significantly enhanced. Although many studies exist involving bulk powders, this is the first work to our knowledge that demonstrates the ability to control and monitor the entry of a molecule into a metal organic framework (MOF) film in situ using temperature. In this case, nanoparticle films of ZIF-8 were prepared and studied in ultrahigh vacuum. The ability to control and monitor surface adsorption versus pore adsorption in situ is key to future fundamental study of MOFs, for example, in the identification of active sites in reaction mechanisms.