Molecule Clustering Dynamics in the Molecular Doping Process of Si(111) with Diethyl-propyl-phosphonate.

The molecular doping (MD) process is based on the deposition of dopant-containing molecules over the surface of a semiconductor substrate, followed by the thermal diffusion step. Previous studies suggest that, during the deposition, the molecules nucleate clusters, and at prolonged deposition times, they grow into self-assembled layers on the sample to be doped. Little is known about the influence of nucleation kinetics on the final properties of these layers and how they change when we modify the solution properties. In this work, we examine the nucleation rate and the molecular surface coverage kinetics of diethyl-propyl phosphonate on silicon at different solution concentrations and how these conditions influence the final electrical properties of the doped samples. We present a high-resolution morphological characterization of the as-deposited molecules together with the electrical results of the final doped samples. The experimental results show a non-obvious behavior, explained through understanding of the competition between the molecules' physisorption and chemisorption mechanisms. As a consequence, due to the deeper knowledge of the deposition phase, a finer tuning of the conductive properties of MD-doped samples is achieved.

Study of the Molecule Adsorption Process during the Molecular Doping.

Molecular Doping (MD) involves the deposition of molecules, containing the dopant atoms and dissolved in liquid solutions, over the surface of a semiconductor before the drive-in step. The control on the characteristics of the final doped samples resides on the in-depth study of the molecule behaviour once deposited. It is already known that the molecules form a self-assembled monolayer over the surface of the sample, but little is known about the role and behaviour of possible multiple layers that could be deposited on it after extended deposition times. In this work, we investigate the molecular surface coverage over time of diethyl-propyl phosphonate on silicon, by employing high-resolution morphological and electrical characterization, and examine the effects of the post-deposition surface treatments on it. We present these data together with density functional theory simulations of the molecules-substrate system and electrical measurements of the doped samples. The results allow us to recognise a difference in the bonding types involved in the formation of the molecular layers and how these influence the final doping profile of the samples. This will improve the control on the electrical properties of MD-based devices, allowing for a finer tuning of their performance.