Per- and polyfluoroalkyl substances (PFAS) have been identified by various regulatory bodies as substances of concern. In line with the objective of safer and sustainable by design, a comprehensive program has been initiated to address these concerns. Part of this program includes the development of non -fluorinated photoacid generators (PAGs) without introducing new chemicals with unintended consequences. Using computational chemistry and synthetic organic chemistry , several scaffolds amenable to PAG library design have been realized. These novel PAGs offer facile tunability and advantages in many critical design parameters such as pKa, diffusion, absorption, shelf-life stability, and scalability. These early generation non-fluorinated PAGs show competitive and similar lithographic performance compared to fluorinated PAGs in i-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser and extreme ultraviolet (EUV) lithography.
As the patterning resolution of semiconductor manufacturing increases, so does the need to remove critical defects from the photochemical supply chain. In particular, metallic contaminants have been known to lead to various types of defects such as cone defects that contribute to significant yield loss 1. Hence, control of metallic contaminants is critical for these next generation lithography processes. Previous work has introduced the Purasol™ LS2 solvent purifier, capable of superior metal reduction in a wide range of photochemical solvents 2. Current work focuses on purification of polymer solutions, a key intermediate material in the photochemical ecosystem. We present data detailing the ability of the LS2 purifier to remove metals from a poly-(4-hydroxystyrene) (PHS) polymer solution. Purifier membrane in coupons as well as an LS2 purifier device are used in a series of experiments to investigate the metal removal efficiency in the polymer solution as a function of various experimental parameters. Metal removal is quantified using ICP-MS (inductively coupled plasma mass spectroscopy) measurements. In addition, we also present customer data demonstrating the effectiveness of the LS2 in purifying polymer solutions to reduce defects that degrade yield performance.
The continued miniaturization of integrated circuit features has been made possible through multilayer patterning processes where different etch steps transfer the patterned photoresist image through various hardmasks to the underlying substrate. Wet etchants, such as the aqueous mixture of ammonium hydroxide and hydrogen peroxide known as SC-1 (Standard Clean -1), are often used for the selective removal of metal surfaces (i.e. TiN) from the substrate. To ensure that this metal removal is indeed selective, organic underlayers are used to protect the metal surface in regions where metal removal is unwanted. Unfortunately, these harsh basic and oxidative conditions are often incompatible with many underlayers which result in their delamination from the substrate, exposing and damaging the metal surface.
Here we report our work on improving the SC-1 wet etch resistance of an underlayer coated over TiN. By increasing the film’s binding to the metal surface and decreasing its brittleness through polymer design or additive choice, we improve the time for film delamination in an SC-1 bath from 1 minute to over 20 minutes. Furthermore, we have developed a new method to evaluate SC-1 resistance by quantifying TiN removal by measuring the amount of titanium leached into the solution during wet etching by using inductively coupled plasma mass spectrometry (ICP-MS). We demonstrate with this method and XSEM images that TiN can be removed if the film does not act as a sufficient barrier to prevent SC-1 penetration, even if no film delamination is observed, which will be used to optimize future underlayer formulations.
Removing metallic contaminants from the photochemical supply chain is critical for the creation of high yielding, highly reliable semiconductors. Metallic contaminants may lead to various types of defects, such as cone defects, that can result in significant yield loss and degraded long-term reliability. This makes control of metallic contaminants even more critical in advanced photolithography processes, where the device reliability demands metal contaminants at parts per trillion (ppt) levels. Previous work3 demonstrated the ability of two purifiers, PurasolTM SP and SN, to reduce the metal contaminants in a variety of organic solvents. In this paper we will discuss our continued work to reduce contamination sources that can contribute to defect formation in photolithography applications.
KEYWORDS: Etching, Absorbance, Carbon, Resistance, System on a chip, Reactive ion etching, Polymers, Image processing, Photoresist materials, Optical lithography
The continued miniaturization of integrated circuit features has been made possible through multilayer patterning processes where different etch steps transfer the patterned photoresist image through various hardmasks and ultimately to the underlying substrate. Spin-on carbons (SOCs) are a type of a solution-dispensable carbon hardmask that can offer excellent resistance to various etch gases for good pattern transfer fidelity, while simultaneously conferring desirable gap fill and planarization properties onto the underlying substrate. We recently reported on the development of a new SOC platform with excellent etch resistance, having a relative reactive ion etch (RIE) rate of 1.08 compared to amorphous carbon. However, one drawback we observed for this polymer was its relatively high absorbance between 400-700 nm which can complicate lithographic alignment. Here we report our work on reducing the absorbance of our SOC platform while maintaining its excellent etch resistance. We identify that the origin of high absorbance is from side reactions that occur during curing and discuss the various polymer modifications or additives that prevent these unwanted processes. We additionally look at any trade-offs that are observed between decreasing absorbance and etch resistance and optimize the SOC’s composition to minimize absorbance while having a minimal effect on its etch resistance.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.