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Macromolecular architecture is a critical parameter when tuning polymer material properties. Although the implementation of non-linear polymers in different applications has grown over the years, polymer grafted surfaces such as nanoparticles have traditionally been composed of linear thermoplastic polymers, with a limited number of examples demonstrating a diversity in polymer architectures. In an effort to combine polymer architecturally dependent material properties with polymer grafted particles (PGPs), as opposed to conventional methods of tuning polymer grafting parameters such as the number of chains per surface area (i.e., polymer graft density), a series of bottlebrush grafted particles were synthesized using surface-initiated ring-opening metathesis polymerization (SI-ROMP). These bottlebrush PGPs are composed of glassy, semi-crystalline, and elastomeric polymer side chains with controlled backbone degrees of polymerization (Nbb) at relatively constant polymer graft density on the surface of silica particles with diameters equaling approximately 160 or 77 nm. Bottlebrush polymer chain conformations, evaluated by measuring the brush height of surface grafted polymer chains in solution and the melt, undergo drastic changes in macromolecular dimensions in different environments. In solution, brush heights increase linearly as a function of Nbb, consistent with fully stretched chains, which is confirmed using cryogenic transmission electron microscopy (Cryo-TEM). Meanwhile, brush heights are consistently at a minimum in the melt, indicative of chains collapsed on the particle surface. The conformational extremes for grafted bottlebrush polymers are unseen in any linear polymer chain systems, highlighting the effect of macromolecular architecture and surface grafting. Bottlebrush grafted particles are an exciting class of materials where diversifying polymer architectures will expand PGP material design rules that harness macromolecular architecture to dictate properties.more » « less
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Free, publicly-accessible full text available December 26, 2025
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GaAs(111)B are commercially available substrates widely used for the growth of van der Waals chalcogenide films. Wafer-scale, high-quality crystalline films can be deposited on GaAs(111)B substrates using molecular beam epitaxy. However, two obstacles persist in the use of GaAs(111)B: first, the surface dangling bonds make it challenging for the growth of van der Waals materials; second, the As-terminated surface is prone to aging in air. This study investigated a thermal treatment method for deoxidizing GaAs(111)B substrates while simultaneously passivating the surface dangling bonds with Se. By optimizing the treatment parameters, we obtained a flat and completely deoxidized platform for subsequent film growth, with highly reproducible operations. Furthermore, through first-principle calculations, we find that the most energetically favorable surface of GaAs(111)B after Se passivation consists of 25% As atoms and 75% Se atoms. Finally, we discovered that the common storage method using food-grade vacuum packaging cannot completely prevent substrate aging, and even after thermal treatment, aging still affects subsequent growth. Therefore, we recommend using N2-purged containers for better preservation.more » « less
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