James R. Sounik

Nonlinear Bragg mirror made from a silicon phthalocyanine/methyl methacrylate copolymer

A nonlinear Bragg mirror based on saturably absorbing nonlinear-optical polymers is proposed and demonstrated. The saturable absorber is a copolymer of silicon phthalocyanine with methyl methacrylate, which exhibits its largest nonlinear absorption near 670 nm. A 23-layer stack was made by spin coating, with polymethyl methacrylate as the low-index layer, and the linear-optical performance was found to agree reasonably well with predictions based on a modified two-level model of the optical properties of the copolymer. Optical limiting at an intensity of 5-10 MW/cm(2) was demonstrated for 6-ns pulses at a wavelength of 688 nm.

Non-chemically amplified 248-nm resist materials

Remarkable progress has been made in the formulation of chemically amplified resists for deep-UV (DUV or 248 nm) lithography. These materials are now in general use in full scale manufacturing. One of the deterrents to rapid and universal adoption of DUV lithography has been the combination of high cost of ownership and a narrow process latitude when compared to conventional i-line process alternatives. A significant part of the high cost of the DUV process is associated with installing and maintaining special air handling equipment that is required to remove basic contaminants from the ambient. Manufacture process latitude demands this special air handling. The chemically amplified resists were developed originally to support mercury lamp powered exposure systems. The sensitivity realized by chemical amplification is required to enable useful productivity with such systems that generate very little DUV flux at the wafer plane. With the advent of high powered excimer laser based illumination systems for 248 nm steppers and step-and-scan systems, it is appropriate to re-examine the applicability of non-chemically amplified DUV resist systems. These systems are less sensitive but have the potential to offer both lower cost of ownership and improved process latitude. A series of photoactive compounds (PACs) have been synthesized and auditioned for use in the formulation of a non-chemically amplified 248 nm resist. The most promising of these materials are analogs of 3-oxo-3-diazocoumarin. This chromophore displays photochemistry that is analogous to that of the diazonaphthoquinones (DNQ) that are the basis of i-line resist formulations, but it bleaches at 248 nm. Several structural analogs of the chromophore have been synthesized and a variety of ballast groups have been studied with the goal of enhancing the dissolution inhibition properties of the molecule. The diazocoumarin PACs have been formulated with customized phenolic resins that were designed to provide the combination of optical transparency, dry etch resistance and the dissolution characteristics that are required for manufacturing applications. The resins are copolymers of poly(4-hydroxystyrene) and blends of these polymers with novolac.

Synthesis and lithographic performance of highly branched polymers from hydroxyphenylmethylcarbinols

A new synthesis pathway for 4- and 2-hydroxymethylcarbinol (4- and 2-HPMC) has made a new class of highly branched polymers readily available. The polymers, which are isomers of polyhydroxystyrene, show unexpected dissolution behavior in aqueous bases which differs from the solubility characteristics seen for the linear polymers obtained by free-radical polymerization. This behavior is traced back to the influence of the changing bond types in the co-polymerization series on the kinetic parameters. With respect to lithography, the absorption of the polymers is too high to make them attractive as DUV resist materials. Although their bond structure shows all bond types that also exist in novolaks, the HPMC polymers are found to be more PHS-like than novolak-like in their performance with DNQ sensitizers. However, they are compatible with DNQ/novolak resists, and can be used in resin blends with novolaks without phase separation.