Atomic precision advanced manufacturing (APAM) leverages the highly reactive nature of Si dangling bonds relative to H- or Cl-passivated Si to selectively adsorb precursor molecules into lithographically defined areas with sub-nanometer resolution. Due to the high reactivity of dangling bonds, this process is confined to ultra-high vacuum (UHV) environments, which currently limits its commercialization and broad-based appeal. In this work, we explore the use of halogen adatoms to preserve APAM-derived lithographic patterns outside of UHV to enable facile transfer into real-world commercial processes. Specifically, we examine the stability of H-, Cl-, Br-, and I-passivated Si(100) in inert N2 and ambient environments. Characterization with scanning tunneling microscopy and x-ray photoelectron spectroscopy (XPS) confirmed that each of the fully passivated surfaces were resistant to oxidation in 1 atm of N2 for up to 44 h. Varying levels of surface degradation and contamination were observed upon exposure to the laboratory ambient environment. Characterization by ex situ XPS after ambient exposures ranging from 15 min to 8 h indicated the Br– and I–passivated Si surfaces were highly resistant to degradation, while Cl–passivated Si showed signs of oxidation within minutes of ambient exposure. As a proof-of-principle demonstration of pattern preservation, a H–passivated Si sample patterned and passivated with independent Cl, Br, I, and bare Si regions was shown to maintain its integrity in all but the bare Si region post-exposure to an N2 environment. The successful demonstration of the preservation of APAM patterns outside of UHV environments opens new possibilities for transporting atomically-precise devices outside of UHV for integrating with non-UHV processes, such as other chemistries and commercial semiconductor device processes.

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Ultradoping introduces unprecedented dopant levels into Si, which transforms its electronic behavior and enables its use as a next-generation electronic material. Commercialization of ultradoping is currently limited by gas-phase ultra-high vacuum requirements. Solvothermal chemistry is amenable to scale-up. However, an integral part of ultradoping is a direct chemical bond between dopants and Si, and solvothermal dopant-Si surface reactions are not well-developed. This work provides the first quantified demonstration of achieving ultradoping concentrations of boron (~1e14 cm 2 ) by using a solvothermal process. Surface characterizations indicate the catalyst cross-reacted, which led to multiple surface products and caused ambiguity in experimental confirmation of direct surface attachment. Density functional theory computations elucidate that the reaction results in direct BÀ Si surface bonds. This proof-of-principle work lays groundwork for emerging solvothermal ultradoping processes.

Self-assembled monolayers (SAMs) on metal and semiconductor surfaces are of interest in electronic devices, molecular and biosensors, and nanostructured surface preparation. Bifunctionalized molecules, where one functional group attaches to the surface while the other remains free for further modification, allow for the rational design of multilayer chemisorbed thin films. In this study, substituted styrenes acted as a model system for SAM formation through an alkene moiety. Substituents ranging from activating to strongly deactivating for aromatic reactions were used to probe the effect of the electronic properties of functionalizing molecules on the rate of SAM formation. Substituted styrene SAMs were formed on hydrogen-terminated p-type Si(100) and n-type Si(111) via sonochemical functionalization. Monolayers were characterized via ellipsometry, IR spectroscopy, contact angle goniometry, and X-ray photoelectron spectroscopy (XPS). Initial rates of reaction for molecules that selectively attached through the alkene were further studied. A linear relationship was observed between the initial rates of surface functionalization and the substituent electron donating/withdrawing ability for the substituted styrenes, as described by their respective Hammett constants. This study provides precedent for applying well quantified homogeneous chemical reaction relationships to reactions at the solid-liquid interface.

Carbene based self-assembled monolayers are demonstrated to be effective supports for forming highly stable surface-mounted metal–organic frameworks on gold substrates.