Reaction of Dichlorophenylborane with H–Si(100)

[Image: see text] Traditional approaches to achieving dopant functionalized Si involve grafting the dopant to the Si substrates through O–Si or C–Si bonds, resulting in indirect attachment of the dopant to the Si. Recently, ultrahigh vacuum work has demonstrated that high densities of direct B–Si bonds enable unprecedented electronic behaviors in Si that make it possible for Si to be used as a next-generation electronic material. As solvothermal approaches are inherently amenable to scale-up, there is currently a push to develop solvothermal approaches for the formation of direct dopant-Si bonds. Thus far, B–Si chemistries for next-generation electronic materials have been demonstrated with boron trichloride and bis(pinacolatodiboron). In this work, we use a combination of experimental work and computational studies to examine the reactivity of a phenyl derivatized boron trichloride, namely dichlorophenylborane, with H–Si(100). We determine that despite the stability and ease for the formation of C–Si bonds, the organic component, the phenyl group remains attached to the B and does not yield competitive formation of products via a Si–C bond. This reaction proved a new solvothermal method for the formation of direct B–Si bonds that, with further work, can be leveraged in developing next-generation electronic materials.