It is the goal of this body of work to research an assortment of different photoacid generators (PAGs) and quantify their ability to perform the decomposition of poly(propylene carbonate) (PPC). Adding PAGs to PPC allows for a decreased polymer decomposition temperature, which can in turn be used as a sacrificial polymer for the fabrication of various microelectromechanical and microfluidic devices. A focus will be placed on relating the properties of the PAG such as acid strength, acid volatility, and PAG activation to processing issues like percentage of total film decomposition, amount and composition of film residue, decomposition rate, decomposition temperature, and environmental dependencies. This research discovered that the use of superacid triflic and nonaflic based PAGs were not adequate for the decomposition of PPC due to the high vapor pressure of the acid. Furthermore, the non-fluorinated sulfonic acid based PAGs do not posses the super-acid level acidity needed to sufficiently decompose PPC. Conversely, a perfluorinated methide and a tetrakis(pentafluoropheyl)borate based PAG both demonstrated the capability for high level PPC decomposition. Building on the knowledge gained through experimentation with these individual PAGs, the creation of a novel Combination PAG was accomplished. The Combination PAG uses acid groups with different physical properties collectively working to achieve what neither could complete individually.

Improvements for Chip-Chip Interconnects and MEMS Packaging Through Materials and Processing Research Erdal Uzunlar 129 Pages Directed by Dr. Paul A. Kohl The work presented in this dissertation focuses on improvements for ever-evolving modern microelectronic technology. Specifically, three topics were investigated in this work: electroless copper deposition on printed wiring boards (PWBs), polymer-based air-gap microelectromechanical systems (MEMS) packaging technology, and thermal stability enhancement in sacrificial polymers, such as poly(propylene carbonate) (PPC). In the electroless copper deposition study, Ag-based catalysts were identified as a low-cost and equally active alternative to expensive Pd-based catalysts. Hot H2SO4 treatment of PWBs was found as a non-roughening surface treatment method to minimize electrical losses. In MEMS packaging study, a sacrificial polymer-based air-gap packaging technique was improved in terms of identification and simplification of air-gap formation process options, optimization of thermal treatment steps, assessing air-gap formation performance, and analyzing the chemical composition of residue. It was found that non-photosensitive PPC leaves less residue, and creates more reliable air-gaps. The mechanical strength of air-gaps was found to come from residual stress in benzocyclobutene (BCB) caps. In thermal stability of PPC study, the mechanism of thermal stability increase on copper (Cu) surfaces was found as the complex formation between Cu(I) and iodonium of the photoacid generator (PAG), leading to hindrance of acid formation by PAG and restriction of acid-catalyzed decomposition of PPC.

This thesis reports on a new low-cost wafer-level packaging technology for microelectromechanical systems (MEMS). The MEMS process is based on a revised version of High Aspect Ratio Polysilicon and Single Crystal Silicon (HARPSS) technology. The packaging technique is based on thermal decomposition of a sacrificial polymer through a polymer overcoat followed by metal coating to create resizable MEMS packages. The sacrificial polymer is created on top of the active component including beams, seismic mass, and electrodes by photodefining, dispensing, etching, or molding. The low loss polymer overcoat is patterned by photodefinition to provide access to the bond pads. The sacrificial polymer decomposes at temperatures around 200-280aC and the volatile products permeate through the overcoat polymer leaving an embedded air-cavity. For MEMS devices that do not need hermetic packaging, the encapsulated device can then be handled and packaged like an integrated circuit. For devices that are sensitive to humidity or need vacuum environment, hermiticity is obtained by deposition and patterning thin-film metals such as aluminum, chromium, copper, or gold. To demonstrate the potential of this technology, different types of capacitive MEMS devices have been designed, fabricated, packaged, and characterized. These includes beam resonators, RF tunable capacitors, accelerometers, and gyroscopes. The MEMS design includes mechanical, thermal, and electromagnetic analysis. The device performance, before and after packaging is compared and the correlation to the model is presented. The following is a summary of the main contributions of this work to the extensive research focused on MEMS and their packaging: 1)A new low-cost wafer-level packaging method for bulk or surface micromachined devices including resonators, RF passives and mechanical sensors is reported. This technique utilizes thermal decomposition of a sacrificial polymer through an overcoat polymer to create buried channels on top of the resonant/movable parts of the micromachined device. It provides small interconnections together with resizable package dimensions. We report MEMS package thicknesses in the range of 10 mm to 1 mm, and package size from 0.0001 mm to 1 mm. 2)A revised version of the HARPSS technology is presented to implement high aspect ratio silicon capacitors, resonators and inertial sensors in the smallest area.

Materials, Processes, and Characterization of Extended Air-gaps for the Intra-level Interconnection of Integrated Circuits Seongho Park 157 pages Directed by Dr. Paul A. Kohl and Dr. Sue Ann Bidstrup Allen The integration of an air-gap as an ultra low dielectric constant material in an intra-metal dielectric region of interconnect structure in integrated circuits was investigated in terms of material properties of a thermally decomposable sacrificial polymer, fabrication processes and electrical performance. Extension of the air-gap into the inter-layer dielectric region reduces the interconnect capacitance. In order to enhance the hardness of a polymer for the better process reliabilities, a conventional norbornene-based sacrificial polymer was electron-beam irradiated. Although the hardness of the polymer increased, the thermal properties degraded. A new high modulus tetracyclododecene-based sacrificial polymer was characterized and compared to the norbornene-based polymer in terms of hardness, process reliability and thermal properties. The tetracyclododecene-based polymer was harder and showed better process reliability than the norbornene-based sacrificial polymer. Using the tetracyclododecene-based sacrificial polymer, a single layer Cu/air-gap and extended Cu/air-gap structures were fabricated. The effective dielectric constant of the air-gap and extended air-gap structures were 2.42 and 2.17, respectively. This meets the requirements for the 32 nm node. Moisture uptake of the extended Cu/air-gap structure increased the effective dielectric constant. The exposure of the structure to hexamethyldisilazane vapor removed the absorbed moisture and changed the structure hydrophobic, improving the integration reliability. The integration processes of the air-gap and the extended air-gap into a dual damascene Cu metallization process has been proposed compared to state-of-the-art integration approaches.