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Fundamental Studies of Copper Corrosion in Interconnect Fabrication Process and Spectroscopic Investigation of Low-k StructuresGoswami, Arindom 12 1900 (has links)
In the first part of this dissertation, copper bimetallic corrosion and its inhibition in cleaning processes involved in interconnect fabrication is explored. In microelectronics fabrication, post chemical mechanical polishing (CMP) cleaning is required to remove organic contaminants and particles left on copper interconnects after the CMP process. Use of cleaning solutions, however, causes serious reliability issues due to corrosion and recession of the interconnects. In this study, different azole compounds are explored and pyrazole is found out to be a potentially superior Cu corrosion inhibitor, compared to the most widely used benzotriazole (BTA), for tetramethyl ammonium hydroxide (TMAH)-based post CMP cleaning solutions at pH 14. Micropattern corrosion screening results and electrochemical impedance spectroscopy (EIS) revealed that 1 mM Pyrazole in 8 wt% TMAH solution inhibits Cu corrosion more effectively than 10 mM benzotriazole (BTA) under same conditions. Moreover, water contact angle measurement results also showed that Pyrazole-treated Cu surfaces are relatively hydrophilic compared to those treated with BTA/TMAH. X-ray photoelectron spectroscopy (XPS) analysis supports Cu-Pyrazole complex formation on the Cu surface. Overall Cu corrosion rate in TMAH-based highly alkaline post CMP cleaning solution is shown to be considerably reduced to less than 1Å/min by addition of 1 mM Pyrazole. In the second part, a novel technique built in-house called multiple internal Reflection Infrared Spectroscopy (MIR-IR) was explored as a characterization tool for characterization of different low-k structures.In leading edge integrated circuit manufacturing, reduction of RC time delay by incorporation of porous ultra low-k interlayer dielectrics into Cu interconnect nanostructure continues to pose major integration challenges. The main challenge is that porous structure renders interlayer dielectrics mechanically weak, chemically unstable and more susceptible to the RIE plasma etching damages. Besides the challenge of handling weak porous ultra low-k materials, a lack of sensitive metrology to guide systematic development of plasma etching, restoration and cleaning processes is the major stumbling block. We explored Multiple Internal Reflection Infrared Spectroscopy and associated IR techniques as a sensitive (sub-5 nm) characterization tool to investigate chemical bonding modification across fluorocarbon etch residues and low-k dielectric interface after plasma etching, ashing, UV curing and post-etch cleaning. The new insights on chemical bonding transformation mapping can effectively guide the development of clean-friendly plasma etch for creating ultra low-k dielectric nanostructures with minimal dielectric damages.
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Interfacial Electrochemistry of Cu/Al Alloys for IC Packaging and Chemical Bonding Characterization of Boron Doped Hydrogenated Amorphous Silicon Films for Infrared CamerasRoss, Nick 05 1900 (has links)
We focused on a non-cooling room temperature microbolometer infrared imaging array device which includes a sensing layer of p-type a-Si:H component layers doped with boron. Boron incorporation and bonding configuration were investigated for a-Si:H films grown by plasma enhanced chemical deposition (PECVD) at varying substrate temperatures, hydrogen dilution of the silane precursor, and dopant to silane ratio using multiple internal reflection infrared spectroscopy (MIR-IR). This study was then confirmed from collaborators via Raman spectroscopy. MIR-IR analyses reveal an interesting counter-balance relationship between boron-doping and hydrogen-dilution growth parameters in PECVD-grown a-Si:H. Specifically, an increase in the hydrogen dilution ratio (H2/SiH4) or substrate temperature was found to increase organization of the silicon lattice in the amorphous films. It resulted in the decrease of the most stable SiH bonding configuration and thus decrease the organization of the film. The new chemical bonding information of a-Si:H thin film was correlated with the various boron doping mechanisms proposed by theoretical calculations. The study revealed the corrosion morphology progression on aluminum alloy (Al, 0.5% Cu) under acidic chloride solution. This is due to defects and a higher copper content at the grain boundary. Direct galvanic current measurement, linear sweep voltammetry (LSV), and Tafel plots are used to measure corrosion current and potential. Hydrogen gas evolution was also observed (for the first time) in Cu/Al bimetallic interface in areas of active corrosion. Mechanistic insight that leads to effective prevention of aluminum bond pad corrosion is explored and discussed.
(Chapter 4) Aluminum bond pad corrosion activity and mechanistic insight at a Cu/Al bimetallic interface typically used in microelectronic packages for automotive applications were investigated by means of optical and scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and electrochemistry. Screening of corrosion variables (temperature, moisture, chloride ion concentration, pH) have been investigated to find their effect on corrosion rate and to better understand the Al/Cu bimetallic corrosion mechanism. The study revealed the corrosion morphology progression on aluminum alloy (Al, 0.5% Cu) under acidic chloride solution. The corrosion starts as surface roughening which evolves into a dendrite structure and later continues to grow into a mud-crack type corrosion. SEM showed the early stage of corrosion with dendritic formation usually occurs at the grain boundary. This is due to defects and a higher copper content at the grain boundary. The impact of copper bimetallic contact on aluminum corrosion was explored by sputtering copper microdots on aluminum substrate. Copper micropattern screening revealed that the corrosion is activated on the Al/Cu interface area and driven by the large potential difference; it was also seen to proceed at much higher rates than those observed with bare aluminum. Direct galvanic current measurement, linear sweep voltammetry (LSV), and Tafel plots are used to measure corrosion current and potential. Hydrogen gas evolution was also observed (for the first time) in Cu/Al bimetallic interface in areas of active corrosion. Mechanistic insight that leads to effective prevention of aluminum bond pad corrosion is explored and discussed. Micropattern corrosion screening identified hydrogen evolution and bimetallic interface as the root cause of Al pad corrosion that leads to Cu ball lift-off, a fatal defect, in Cu wire bonded device. Complete corrosion inhibition can be achieved by strategically disabling the mutually coupled cathodic and anodic reaction cycles.
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