Reaction of Dichlorophenylborane with H-Si(100)

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.