Pyrite (FeS2) nanocrystals with a narrow size distribution and optical absorption from 1600 to 380 nm were synthesized in a single stage by reacting ferrous chloride with elemental sulfur in oleylamine (OAm) without an additional ligand. X-ray diffraction, Raman, and scanning electron microscopy showed that pyrite cubes with dimensions of 88 ± 14 nm formed at 200 °C, an S to Fe ratio of 6, and 1 h reaction time in OAm. The time required to form phase pure pyrite depended on the S to Fe ratio. Phase purity was obtained in less than 1 h at a ratio of 6, but times as long as 24 h were necessary at a ratio of 2.75. The rate of pyrite formation increased with higher sulfur concentrations, which shows that molecules containing sulfur are involved in the rate-determining step. Both H2S and polysulfides of the form S n 2– are known to form in oleylamine. The slow step is the reaction between FeS and these molecules. Fe2+S2– undergoes nucleophilic attack by H2S and S n 2–; S2– converts to S– and sulfur is transferred forming pyrite Fe2+S2 2–.

The effect of two different commercially-available CVD-coated diamond conditioning discs on copper CMP was investigated tribologically and kinetically with the intent of correlating pad surface micro-texture to polish performance. Data analyses were particularly focused on in-situ shear and normal force measurements taken during polishing at several pressures (P) and sliding velocities (V), including Fast Fourier Transform (FFT) analysis of the data. One of the two discs consistently resulted in greater variances of shear force with increasing P and V indicative of increased pad-slurry-wafer stick-slip events. This trend correlated to higher values of coefficient of friction (COF) and removal rate (RR). By dividing the shear force variance by the normal force variance, a new parameter, termed directivity, was used to further emphasize the improved performance of the above-mentioned disc. Lastly, the tribological and kinetic data, combined with data regarding the pad's micro-texture and its extent of contact with the wafer, showed that at all values of P and V, higher values of directivity correlated to more contacting pad asperities, a greater asperity density and a thinner micro hydrodynamic lubrication layer, thus highlighting the potential importance of directivity in future studies.

Previous studies have shown that spectral analysis based on force data can elucidate fundamental physical phenomena during chemical mechanical planarization (CMP). While it has not been literally described elsewhere, such analysis was partly motivated by modern violinmakers and physicists studying Old Italian violins, who were trying to discover spectral relations to sound quality. In this paper, we draw parallels between violins and CMP as far as functionality and spectral characteristics are concerned. Inspired by the de facto standard of violin testing via hammer strikes on the base edge of a violin’s bridge, we introduce for the first time, a mobility plot for the polisher by striking the wafer carrier head of a CMP polisher with a hammer. Results show three independent peaks that can indeed be attributed to the polisher’s natural resonance. Extending our study to an actual CMP process, similar to hammered and bowed violin tests, at lower frequencies the hammered and polished mobility peaks are somewhat aligned. At higher frequencies, peak alignment becomes less obvious and the peaks become more isolated and defined in the case of the polished wafer spectrum. Lastly, we introduce another parameter from violin testing known as directivity, Δ, which in our case, we define as the ratio of shear force variance to normal force variance acquired during CMP. Results shows that under identical polishing conditions, Δ increases with the polishing removal rate.

SiGe 25% substrates were treated with aqueous solutions of ammonium sulfide with and without added acid to understand the adsorption of sulfur on the surface. X-ray photoelectron spectroscopy showed no sulfide layer was deposited from aqueous (NH 4 ) 2 S alone and instead both Si and Ge oxides formed during immersion in the sulfur solution. The addition of hydrofluoric and hydrochloric acids dropped the pH from 10 to 8 and deposited sulfides, yet increased the oxide coverage on the surface and preferentially formed Ge oxides. The sulfur coverage grew with increasing concentrations of acid in the aqueous (NH 4 ) 2 S. The simultaneous deposition of O and S is suspected to be the result of oxidized sulfur species in solution. Metal-insulator-semiconductor capacitor (MISCAP) devices were fabricated to test the electrical consequences of aqueous ammonium sulfide wet chemistries on SiGe. MISCAPs treated with acidic ammonium sulfide solutions contained fewer interface defects in the valence band region. The defect density (D it ) was on the order of 10 þ12 cm -2 eV À1. The flat band voltage shift was lower after the acidic ammonium sulfide treatment, despite the presence of surface oxides. Adsorption of S and potentially O improved the stability of the surface and made it less electrically active.

In-situ conditioning is known to increase material removal rate (RR) during chemical mechanical planarization (CMP), because it roughens the pad surface that is in contact with the wafer. Previous studies have shown that the conditioning disc changes the pad surface micro-texture and affects the thermal, kinetic and tribological attributes of the CMP process. This study focuses on two different diamond discs for in-situ conditioning during tungsten CMP, and shows how real-time force data improves our understanding of the effects from using one disc versus the other. Shear and normal forces were analyzed through spectral analysis, variance and force scatter plots. Frequency signatures that appear regardless of the type of disc used were likely attributed to vibrations of the polisher and the harmonics of these vibrations. A new parameter, directivity ( ), was employed, which highlighted the significant differences in shear force variance between the two discs. Above all, this study confirmed that high correlated with high RR.Compared to a related study on copper CMP with these discs, the trends between and RR seemed to continue to hold.