Lowering the Environmental Impact Of High-κ/Metal Gate Stack Surface Preparation Processes

摘要

Hafnium based oxides and silicates are promising high-κ dielectrics to replace SiO₂ as gate material for state-of-the-art semiconductor devices. However, integrating these new high-κ materials into the existing complementary metal-oxide semiconductor (CMOS) process remains a challenge. One particular area of concern is the use of large amounts of HF during wet etching of hafnium based oxides and silicates. The patterning of thin films of these materials is accomplished by wet etching in HF solutions. The use of HF allows dissolution of hafnium as an anionic fluoride complex. Etch selectivity with respect to SiO₂ is achieved by appropriately diluting the solutions and using slightly elevated temperatures. From an ESH point of view, it would be beneficial to develop methods which would lower the use of HF. The first objective of this study is to find new chemistries and developments of new wet etch methods to reduce fluoride consumption during wet etching of hafnium based high-κ materials. Another related issue with major environmental impact is the usage of large amounts of rinsing water for removal of HF in post-etch cleaning step. Both of these require a better understanding of the HF interaction with the high-κ surface during the etching, cleaning, and rinsing processes. During the rinse, the cleaning chemical is removed from the wafers. Ensuring optimal resource usage and cycle time during the rinse requires a sound understanding and quantitative description of the transport effects that dominate the removal rate of the cleaning chemicals from the surfaces. Multiple processes, such as desorption and re-adsorption, diffusion, migration and convection, all factor into the removal rate of the cleaning chemical during the rinse. Any of these processes can be the removal rate limiting process, the bottleneck of the rinse. In fact, the process limiting the removal rate generally changes as the rinse progresses, offering the opportunity to save resources. The second objective of this study is to develop new rinse methods to reduce water and energy usage during rinsing and cleaning of hafnium based high-κ materials in single wafer-cleaning tools. It is necessary to have a metrology method which can study the effect of all process parameters that affect the rinsing by knowing surface concentration of contaminants in patterned hafnium based oxides and silicate wafers. This has been achieved by the introduction of a metrology method at The University of Arizona which monitors the transport of contaminant concentrations inside micro- and nano- structures. This is the only metrology which will be able to provide surface concentration of contaminants inside hafnium based oxides and silicate micro-structures while the rinsing process is taking place. The goal of this research is to study the effect of various process parameters on rinsing of patterned hafnium based oxides and silicate wafers, and modify a metrology method for end point detection.