Ratnam Sooriyakumaran

Novel thin film composite membrane containing ionizable hydrophobes: pH-dependent reverse osmosis behavior and improved chlorine resistance

New polyamide thin film composite membranes were prepared by interfacial polymerization of hexafluoroalcohol (HFA)-containing aromatic diamine and trimesoyl chloride (TMC) on a porous polysulfone support. The surface properties of the resulting membranes were characterized by water contact angle, XPS, and SEM. Additionally, the desalination separation performance was evaluated by the cross-flow filtration of 2000 ppm NaCl solution. Water contact angle and XPS analyses indicated that the HFA-containing polyamide membrane is relatively hydrophobic at neutral conditions but becomes hydrophilic at basic conditions due to ionization of the HFA groups, so we refer to this group as an “ionizable hydrophobe” or “i-phobe”. The membrane showed strongly pH-dependent reverse osmosis behavior with enhanced performance (high water flux and high salt rejection) at high pH (ca. 10). Both the electron withdrawing nature and the steric bulkiness of the HFA functionality are also advantageous in protecting the polyamide membrane from chlorine attack. Based upon NMR studies of model polymers (linear polyamides with and without the HFA functionality) and the membrane performance measured before and after chlorine exposure, the HFA-containing polyamide has improved chlorine stability compared to the reference polyamide made from m-phenylenediamine and TMC.

Antiadhesion considerations for UV nanoimprint lithography

Low surface energy fluorosilane layers are widely used as release coatings for quartz templates in UV nanoimprint lithography, yet they are generally found to degrade with use. It is found that these layers are chemically attacked when used with UV cured methacrylate and vinyl ether resists, as found previously for acrylate resists, leading to the conclusion that low reactivity and not low surface energy is of importance for effective release layers. It is shown that an ion-beam deposited diamondlike carbon release coating is a useful alternative, having both stability in a reactive environment and lower adhesion despite its higher surface energy.

Line edge roughness reduction by plasma curing photoresists

Photoresist line edge roughness (LER) has been highlighted to have an adverse impact on device performance whereas post-etch LER is probably the more relevant metric. Post-etch LER can be reduced by migrating to thicker photoresist films or developing etch processes that are accompanied with lower energy ion bombardment. However, the photoresist and etching processes chosen might have desirable attributes and therefore cannot be changed, e.g. large process window or minimal nested-isolated feature etch bias. In this paper, we demonstrate the reduction of LER at the polysilicon gate level by an inexpensive treatment prior to etch. This HBr plasma treatment can be performed in the main etch chamber with minimal impact on wafer throughput. As a result, during the following etch steps, the photoresist mask is more homogeneous from an etch perspective which in turn helps lower the final LER. In addition, results from blanket etch studies on the various photoresist component films are shown. FTIR spectra of unetched and etched films are compared to demonstrate the preferential etching of certain photoresist/polymer components. The large differences observed in the unetched and etched film surface roughness values for certain photoresist components is postulated as an important source of final LER.

Toward controlled resist line-edge roughness: material origin of line-edge roughness in chemically amplified positive-tone resists

Material origin of resist line edge roughness (LER) in positive-tone chemically amplified resists has been investigated by designing experiments to mimic the composition and the morphology of the resists in the line edge regions where the resist consists of both the protected polymer and its de-protected counterparts. Blends of the protected and the de-protected base polymers for two silicon containing, positive-tone chemically amplified resists were prepared. Morphology and surface roughness of thin films of the polymer blends were probed with atomic force microscope (AFM). AFM results clearly showed that the protected polymer and its de- protected counterparts form distinct phase separated morphology after spin coating and baking. This phase separation leads to surface roughening of the blend films. Furthermore, the surface roughness of the blend films is enhanced after development with an aqueous TMAH developer. These results suggest that the material origin of resist LER in positive-tone chemically amplified resists stems from the compositional heterogeneity due to phase incompatibility of the protected base polymer and its de-protected counterparts in the line edge regions. The effects of blend composition, the extent of de-protection, and processing conditions on the morphology and surface roughness will be presented. The implications of these findings for high-resolution resist design will also be discussed.

Protecting groups for 193-nm photoresists

Two versions of 193-nm single layer resists based on acrylic polymer chemistry have been described previously. The version 1 resist is a tool-testing version and is based on a methacrylate terpolymer structure. Its etch resistance analogue (version 2 resist) contains alicyclic compounds attached to the acrylic backbone. Key to enabling the performance of version 2 resist are the use of steroid additives which behave principally as thermomechanical modifiers to improve the mechanical properties of these rigid polymers through plasticization. We used the tertiary-butyl ester protecting group in these resists for thermal stability and other considerations. This paper describes an investigation of the impact of acid-cleavable protecting group structure on the properties of a series of model acrylic polymers. In this investigation, factors such as thermochemical stability, reactivity to photogenerated acid, and dissolution properties of exposed films as a function of dose were examined. A new highly reactive protecting group is introduced in this study, the tetrahydrofuranyl ester (THF) of methacrylic acid. Additionally, we introduce a new polymer family (polynorbornenes) with superior etch resistance, significantly broadening the polymer chemistry available for the construction of new 193-nm photoresists.

Fluoro-alcohol materials with tailored interfacial properties for immersion lithography

Immersion lithography has placed a number of additional performance criteria on already stressed resist materials. Much work over the past few years has shown that controlling the water-resist interface is critical to enabling high scan rates (i.e. throughput) while minimizing film pulling and PAG extraction (i.e. defectivity). Protective topcoat polymers were developed to control the aforementioned interfacial properties and emerged as key enablers of 193 nm immersion lithography. Achieving the delicate balance between the low surface energies required for high water contact angles (generally achieved via the incorporation of fluorinated groups) and the base solubility required for topcoat removal is challenging. More recently, additional strategies using fluoropolymer materials to control the water-resist interface have been developed to afford topcoat-free resist systems. In our explorations of fluoroalcohol-based topcoat materials, we have discovered a number of structure-property relationships of which advantage can be taken to tailor the interfacial properties of these fluorinated materials. This paper will address the effect of structure on immersion specific properties such as water contact angle, aqueous base contact angle, and dissolution rate.

High-resolution 248-nm bilayer resist

Bilayer thin film imaging is one approach to extend 248 nm optical lithography to 150 nm regime and beyond. In this paper, we report our progress in the development of a positive-tone bilayer resist system consisting of a thin silicon containing imaging layer over a recently developed crosslinked polymeric underlayer. The chemically amplified imaging layer resist is based on a novel dual-functional silicon containing monomer, tris(trimethylsilyl)silylethyl methacrylate, which in addition to providing etch resistance, also functions as the acid sensitive functionality. The stabilization of (beta) -silyl carboncation by silicon allows this moiety to serve as an acid sensitive protecting group. Thus high silicon content and high resist contrast are achieved simultaneously. Lithographic evaluation of the bilayer resist with a 0.63 NA and a 0.68 NA 248 nm exposure tool has demonstrated resolution down to 125 nm equal line/space features with a dose latitude of 16 percent and depth of focus (DOF) of 0.6 um. The dose latitude and DOF for 150 nm equal line/space features are 22 percent and 1.2 um, respectively. Finally, residue-free, ultra-high aspect ratio resist features have been obtained by O2 or O2/SO2 reactive ion etching using a high-density plasma etch system. The resist design, deprotection chemistry, lithographic and etch characteristics of the top layer, as well as the design of the new underlay, will be discussed.

IBM 193-nm bilayer resist: materials, lithographic performance, and optimization

193nm lithography will be the future technology for sub- 150nm resolution. As the dimensions get smaller, resist thickness is also needed to be reduced for better resolution and wider process window. Single layer 193nm resist, with thickness of less than 500nm, may not be able to satisfy some of the substrate etch requirement. With bilayer resist scheme, the thin resist offers the advantages of high resolution and good process window. The thick underlayer provides the etch resistance required for substrate etching. IBM has developed a silane substituted alternating copolymer based 193nm bilayer resist system and demonstrates sub-120nm resolution using Nikon 0.6NA stepper with Chrome on Glass (COG) mask. Lithographic performance and formulation optimizations of this 193nm bilayer resist as well as underlayer evaluation and some etch study will be discussed.

Positive bilayer resists for 248- and 193-nm lithography

We have designed and developed new silicon containing methacrylate monomers that can be used in bilayer resist systems. New monomers were developed because the commercially available silicon monomers were found to be unsuitable for our applications. During the course of the investigation we determined that these monomers were acid labile. We have developed a high resolution DUV bilayer resist system based on these monomers. Although most of our work was concentrated on 248 nm lithography, we have demonstrated that this chemistry can be extended to 193 nm applications.

Extension of 248-nm optical lithography: a thin film imaging approach

A negative-tone bilayer thin film imaged (TFI) resist has been developed for extension of 248 nm optical lithography to sub-150 nm regime. The bilayer TFI resist system consists of a thin (0.2 um) silicon containing top imaging layer and a thick (0.7 - 0.8 um) highly absorbing organic underlayer. The chemically amplified negative-tone top layer resist comprises of three major components: an aqueous base soluble silicon containing polymer, poly(hydroxybenzylsilsesquioxane); a crosslinking agent; and a photoacid generator. The highly absorptive underlayer is a hard baked novolak resist or a DUV ARC. Imaging of the top layer resist has shown resolutions down to 137.5 nm for line/space features and 130 nm for isolated features with 248 nm exposure tools and chrome on glass masks. The O2 reactive ion etch (RIE) selectively of the top layers versus a novolak underlayer is more than 25:1 as a result of the high silicon content in the silicon containing polymer. Furthermore, residue-free and nearly vertical wall profile image transfer to the underlayer has been achieved with RIE. Application of the negative-tone bilayer resist to 150 nm Gbit DRAM critical level lithography has been demonstrated. Resist line edge roughness is also discussed.