Papers by Author: Srini Raghavan

Abstract: Radical formation and detection in aqueous solutions under acoustic irradiation are important during wet cleaning processes in semiconductor industries. Oxidizing radicals such as hydroxyl and hydroperoxyl radicals have been widely studied and characterized using fluorescence and chemiluminescence methods. Hydrogen radicals, which are strongly reducing in nature, have not received much attention. In this study, the rate of hydrogen radical generation in a megasonic field (0.93 MHz) was measured using an electrochemical technique. Specifically, the method is based on the reduction of cupric ions to cuprous chloride complex by the hydrogen radicals in the presence of an excess of chloride ions. This is followed by chronoamperometric determination of the oxidation of cuprous chloride complex back to cupric ions. Hydrogen radical generation rate was measured at different megasonic power densities.

Abstract: Acoustic cavitation, especially transient cavitation, in solutions is accompanied by a number of physical and chemical effects. Due to high temperature and pressure conditions inside bubbles at their collapse, excitation of various species as well as formation of radicals occurs in solution [1-4]. Water molecules excited by megasonic irradiation typically dissociate to hydrogen and hydroxyl radicals (H• and OH•) [5]. The hydroxyl radical is a strong oxidant while the hydrogen radical has reducing properties. In presence of O₂ in the solution, H• reacts with O₂ to form hydroperoxyl (HO₂•) radicals, which act as a reducing as well as a (weak) oxidizing agent [6]. Dissociation of hydroperoxyl radicals result in the formation of superoxide anion radicals (O₂•^-) as follows [6]:

Abstract: Light emission in sound-irradiated liquids, known as Sonoluminescence (SL), is associated with the phenomenon of cavitation that affects wafer damage during megasonic processing of wafers. It has been shown that the intensity of SL can be substantially decreased through the dissolution of carbon dioxide in deionized water. However, such dissolution decreases the pH to roughly 4.0, which is not very desirable for the removal of contaminant particles. This paper reports two chemical systems that are capable of taking advantage of the effect of CO₂ while allowing the use of slightly higher pH values. Specifically, NH₄OH/CO₂ and NH₄HCO₃/dilute HCl systems have been shown to be capable of well controlled reduction in SL at pH 5.7 or 7.0. In order to test whether the free radical scavenging ability of CO₂ may be responsible for its strong SL-inhibitory effect, the effect of a well known free radical scavenger, dimethyl sulfoxide (DMSO), on SL produced in DI water has been investigated.

Abstract: Removal of gold particles (40 nm and 100 nm) from fused silica and thermal oxide surfaces in dilute ammonium hydroxide solutions has been investigated. The particle removal efficiency (PRE) from fused silica surface has been found to be a strong function of ammonium hydroxide concentration and bath temperature. PRE increases from 0 to 85 % with increase in bath temperature from 30 to 80 °C for ammonium hydroxide concentration of 1 %. Addition of megasonic energy to the ammonium hydroxide bath at 30 °C has also shown to improve the PRE significantly. In the case of thermal oxide, the removal of gold particles is much easier compared to that from fused silica. Even for cleaning at 30 °C, the PRE for oxide surface increases from 10 to 90 % with increase in ammonium hydroxide concentration from 0 % to 4 %. Atomic force microscopy measurements reveal that an adhesion force of 10 mN/m exists between fused silica and gold particles in 4 % ammonium hydroxide solution as opposed to only repulsive force in the case of thermal oxide.