Dynamics of ion bombardment-induced modifications of Si(001) at the radio-frequency-biased electrode in low-pressure oxygen plasmas: In situ spectroscopic ellipsometry and Monte Carlo study

Abstract

Low-pressure O2 plasma exposures were performed on c-Si(001) at a radio frequency (rf)-powered electrode in the presence of substrate self-biasing (VB) from VB=−60to−600V, in order to evaluate ion-surface interactions at the growth surface under ion bombardment conditions suitable for the fabrication of high quality optical coatings. The plasma-surface interactions were monitored in situ using real-time spectroscopic ellipsometry (RTSE), which reveals time- and ion-fluence-resolved information about depth-dependent modifications, such as damage and oxidation below the c-Si substrate surface. RTSE analysis indicates almost immediate damage formation (⪡1s) to a depth of a few nanometers below the surface after exposure to a low oxygen ion fluence (∼5×1014Ocm−2). Oxide growth is detected at intermediate fluence (∼1015–1016Ocm−2) and is attributed to O subplantation (shallow implantation); it forms near the surface of the target on top of an O-deficient interfacial damage layer (DL). Both layers experience a self-limiting growth behavior at high fluence (>1017cm−2) as oxide and DL thicknesses reach bias-dependent steady-state values, determined by the maximum ion penetration depth, which increases from ∼3.6to9.5nm for VB=−60to−600V. The in situ experimental study was complemented by Monte Carlo TRIDYN simulations based on the binary collision approximation, which were modified to calculate dynamic changes in the composition of a target exposed to a broad-energy ion source (rf plasma source) at high fluence. Simulation results are found to agree exceptionally well with experiment. In addition, they reveal that the 1.2–3.5-nm-thick DL formed in the steady-state regime is a result of (1) damage formation due to the presence of a small number of high energy O+ ions in the plasma environment, capable of penetrating and damaging up to 3nm deeper than the majority ion population (O2+), and (2) because of important surface motion resulting from oxidation-induced swelling (at low fluence) and sputtering-induced recession (at high fluence). Surface motion in general is found to inhibit oxygen incorporation at high depth in the substrate, thus forming the O-deficient DL. We discuss the implications of these findings on optical coatings deposition and propose a growth mechanism for coatings subjected to intense ion bombardment.