Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Abstract Over the last three decades reactions of organic and organometallic compounds on silicon surfaces have been of great interest. This interest has been fueled by potential applications of such modification approaches to form stable coatings, to improve adhesion properties of organic and inorganic films on semiconductors, and to design suitable molecular electronics components. Despite enormous amount of work on chemistry of various compounds on silicon surfaces, the major driving force behind selective assembly and molecular ordering on reactive silicon surfaces and the preference for chemical reactivity of multifunctional compounds, have never before been a subject of a comprehensive review. As more complex molecular building blocks for multiple applications become available, there is a need to understand and quantify chemical handles on how to manipulate surface reactions in such a way that highly selective processes would take place. Classical kinetics and thermodynamics approaches to surface modification will be the main focus of this review. A large number of well-developed and well-understood reactions on silicon surfaces combined with better computational approaches to describe multiple surface reaction pathways will now allow us to predict, in many cases quantitatively, the selectivity of surface reactions in a variety of experimental conditions. In the past few years numerous examples of these approaches have been published. They provide a foundation for the general understanding and prediction of the chemical properties of a variety of multifunctional compounds. Most importantly, such predictions will be further used to optimize chemical modification processes both in a research laboratory and on the industrial scale. The current review will focus on the chemical control of the selectivity in reactions of multifunctional organic and organometallic molecules on silicon substrates. After a very brief review of the potential monofunctional candidate reactions and a summary of the experimental conditions, the balance of kinetic and thermodynamic factors will be discussed and the application and prediction of surface selectivity will be outlined. The examples of selective surface modification will be further considered on the most common silicon surfaces: Si(100) and Si(111), as well as on partially hydrogenated silicon substrates. Finally, some future directions for the development and the use of multifunctional compounds on silicon will be extended into the third dimension.