To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for …

Experimental mole fraction solubilities of several carboxylic acids (2-methoxybenzoic acid, 4-methoxybenzoic acid, 4-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid,2-methylbenzoic acid and ibuprofen) and 9-fluorenone, thianthrene and xanthene were measured in a wide range of solvents of varying polarity and hydrogen-bonding characteristics. Results of these measurements were used to calculate gas-to-organic solvent and water-to-organic solvent solubility ratios, which were then substituted into known Abraham process partitioning correlations. The molecular solute descriptors that were obtained as the result of these computations described the measured solubility data to within an average absolute deviation of 0.2 log units. The calculated solute descriptors also enable one to estimate many chemically, biologically and pharmaceutically important properties for the ten solutes studied using published mathematical correlations.

Two major topics that involve synthetic strategies to enhance the phosphorescence of organic and inorganic luminophores have been investigated. The first topic involves, the photophysical and photochemical properties of the gold (I) complexes LAuIX (L = CO, RNC where R = alkyl or aryl group; X = halide or pseudohalide), which have been investigated and found to exhibit Au-centered phosphorescence and tunable photochemical reactivity. The investigations have shown a clear relationship between the luminescence energies and association modes. We have also demonstrated for the first time that aurophilic bonding and the ligand p-acceptance can sensitize the photoreactivity of Au(I) complexes. The second topic involves conventional organic fluorophores (arenes), which are made to exhibit room-temperature phosphorescence that originates from spin-orbit coupling owing to either an external or internal heavy atom effect in systematically designed systems that contain d10 metals. Facial complexation of polycyclic arenes to tris[{m-(3,4,5,6-tetrafluorophenylene)}mercury(II)], C18F12Hg3 (1) results in crystalline adducts that exhibit bright RGB (red-green-blue) phosphorescence bands at room temperature. This arene-centered phosphorescence is always accompanied by a reduction of the triplet excited state lifetime due to its sensitization by accelerating the radiative instead of the non-radiative decay. The results of both topics are significant for rational design of …

Copper under-potential deposition (UPD) on iridium was studied due to important implications it presents to the semiconductor industry. Copper UPD allows controlled superfilling on sub-micrometer trenches; iridium has characteristics to prevent copper interconnect penetration into the surrounding dielectric. Copper UPD is not favored on iridium oxides but data shows copper over-potential deposition when lower oxidation state Ir oxide is formed. Effect of anions in solution on silver UPD at platinum (Pt) electrodes was studied with the electrochemical quartz crystal microbalance. Silver UPD forms about one monolayer in the three different electrolytes employed. When phosphoric acid is used, silver oxide growth is identified due to presence of low coverage hydrous oxide species at potentials prior to the monolayer oxide region oxide region.

Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.

Homogeneous hydrogels made of an interpenetrating network of poly(N-isopropylacrylamide) (PNIPAm) and poly(acrylic acid) (PAAc) are synthesized by a two-step process; first making PNIPAm hydrogels and then interpenetrating acrylic acid throughout the hydrogel through polymerization. The kinetic growth of the IPN is plotted and an equation is fitted to the data. When diluted to certain concentrations in water, the hydrogels show reversible, inverse thermal gelation at about 34°C. This shows unique application to the medical field, as the transition is just below body temperature. A drug release experiment is performed using high molecular weight dyes, and a phase diagram is created through observation of the purified, concentrated gel at varying concentrations and temperatures.