First Advisor

Shankar B. Rananavare

Date of Publication


Document Type


Degree Name

Doctor of Philosophy (Ph.D.) in Chemistry






Interconnects (Integrated circuit technology), Semiconductors -- Etching, Thin films -- Corrosion, Copper -- Corrosion



Physical Description

1 online resource (xxv, 198 p.) : ill. (some col.)


As multistep, multilayer processing in semiconductor industry becomes more complex, the role of cleaning solutions and etching chemistries are becoming important in enhancing yield and in reducing defects. This thesis demonstrates successful formulations that exhibit copper and tungsten compatibility, and are capable of Inter Layer Dielectric (ILD) cleaning and selective Ti etching. The corrosion behavior of electrochemically deposited copper thin films in deareated and non-dearated cleaning solution containing hydrofluoric acid (HF) has been investigated. Potentiodynamic polarization experiments were carried out to determine active, active-passive, passive, and transpassive regions. Corrosion rates were calculated from tafel slopes. ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Interestingly, the presence of hydrogen peroxide in the cleaning solution led to more than an order of magnitude suppression of copper dissolution rate. We ascribe this phenomenon to the formation of interfacial CuO which dissolves at slower rate in dilute HF. A kinetic scheme involving cathodic reduction of oxygen and anodic oxidation of Cu0 and Cu+1 is proposed. It was determined that the reaction order kinetics is first order with respect to both HF and oxygen concentrations. The learnings from copper corrosion studies were leveraged to develop a wet etch/clean formulation for selective titanium etching. The introduction of titanium hard-mask (HM) for dual damascene patterning of copper interconnects created a unique application in selective wet etch chemistry. A formulation that addresses the selectivity requirements was not available and was developed during the course of this dissertation. This chemical formulation selectively strips Ti HM film and removes post plasma etch polymer/residue while suppressing the etch rate of tungsten, copper, silicon oxide, silicon carbide, silicon nitride, and carbon doped silicon oxide. Ti etching selectivity exceeding three orders of magnitude was realized. Surprisingly, it exploits the use of HF, a chemical well known for its SiO2 etching ability, along with a silicon precursor to protect SiO2. The ability to selectively etch the Ti HM without impacting key transistor/interconnect components has enabled advanced process technology nodes of today and beyond. This environmentally friendly formulation is now employed in production of advanced high-performance microprocessors and produced in a 3000 gallon reactor.


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