LAUSR

We investigated synthetic strategies for the functionalization of Si(111) surfaces with organic species containing amine moieties. We employed the functionalized surfaces to chemically "glue" perovskites to silicon with efficient electron transfer and minimal oxidation leading to deleterious recombination at the silicon substrate. A two-step halogenation-alkylation reaction produced a mixed allyl-methyl monolayer on Si(111). Subsequent reactions utilized multiple methods of brominating the allyl double bond including reaction with HBr in acetic acid, HBr in THF, and molecular bromine in dichloromethane. Reaction with ammonia in methanol effected conversion of the bromide to the amine. X-ray photoelectron spectroscopy (XPS) quantified chemical states and coverages, transient-microwave photoconductivity ascertained photogenerated carrier lifetimes, atomic force microscopy (AFM) quantified perovskite-silicon adhesion, and nonaqueous photoelectrochemistry explored solar-energy-conversion performance. The HBr bromination followed by the amination yielded a surface with ∼10% amine sites on the Si(111) with minimal oxide and surface recombination velocity values below 120 cm s-1, following extended exposures to air. Importantly, conversion of amine sites to ammonium and deposition of methylammonium lead halide via spin coating and annealing did not degrade carrier lifetimes. AFM experiments quantified adhesion between perovskite films and alkylammonium-functionalized or native-oxide silicon surfaces. Adhesion forces/interactions between the perovskite and the alkylammonium-functionalized films were comparable to the interaction between the perovskite and native-oxide silicon surface. Photoelectrochemistry of perovskite thin films on alkylammonium-functionalized n+-Si showed significantly higher Voc than n+-Si with a native oxide when in contact with a nonaqueous ferrocene+/0 redox couple. We discuss the present results in the context of utilizing molecular organic recognition to attach perovskites to silicon utilizing organic linkers so as to inexpensively modify silicon for future tandem-junction photovoltaics.