Herein, we present a straightforward CuBr-mediated surface-initiated controlled radical polymerization (SI-CRP) method for fabricating polymer brushes using microliter volumes of reaction solution in air and at room temperature. The key advantage of this method is its ability to rapidly grow polymer brushes with oxygen tolerance, driven by the controlled disproportionation of CuI into CuII and Cu0 by CuBr and ligand. We demonstrate the successful preparation of homo-, block, patterned, and wafer-scale polymer brushes. Additionally, the catalyst in CuBr-mediated SI-CRP is reusable, long-lasting, and compatible with various monomers. This work broadens the potential of CuBr for polymer brush growth, making it accessible to both experts and non-experts.
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