Historically, in the mass production of semiconductor devices, exposure tools have been repeatedly replaced with those with a shorter wavelength to meet the resolution requirements projected in the International Technology Roadmap for Semiconductors issued by the Semiconductor Industry Association. After ArF immersion lithography, extreme ultraviolet (EUV; 92.5 eV) radiation is expected to be used as an exposure tool for the mass production at or below the 22 nm technology node. If realized, 92.5 eV EUV will be the first ionizing radiation used for the mass production of semiconductor devices. In EUV lithography, chemically amplified resists, which have been the standard resists for mass production since the use of KrF lithography, will be used to meet the sensitivity requirement. Above the ionization energy of resist materials, the fundamental science of imaging, however, changes from photochemistry to radiation chemistry. In this paper, we review the radiation chemistry of materials related to chemically amplified resists. The imaging mechanisms from energy deposition to proton migration in resist materials are discussed.

Laser-induced and matrix-free desorption/ionization on various submicrometer structures was investigated. First, to examine the effect of surface roughness on ionization, a silicon wafer or stainless steel was scratched with sandpaper. The fluences of a 337-nm nitrogen laser, required for ionization of synthetic polymers and reserpine, were markedly reduced on the scratched stainless steel or silicon as compared to the corresponding untreated surface. Next, arrays of submicrometer grooves, which had been lithographically fabricated on a silicon wafer, yielded protonated angiotensin, and the morphologic orientation demonstrated the positive relation between the laser and groove directions for promoting ionization. The fabricated structure also suggested the submicrometer, but not smaller, or nanometer, structures to be a key factor in direct desorption/ionization on rough surfaces. Finally, submicrometer porous structures of alumina or polyethylene yielded intense molecular ion signals of angiotensin and insulin, in response to direct UV irradiation, when the surface was coated with Au or Pt. The coating provided the additional advantage of prolonged activity for a porous alumina chip, exceeding a month even when the chip was left in the open air. These results indicate that laser-induced desorption/ionization of organic compounds can be implemented on submicrometer structures with an Au- or Pt-coated surface irrespective of the basal materials.

In chemically amplified resists that utilize acid-catalytic reactions for pattern formation, proton dynamics is important from the viewpoints of the insoluble layer formation due to acid loss, the resolution decrease due to acid diffusion, and the image quality improvement due to base-quencher effects. For electron-beam lithography, the protons and anions of the acid are initially generated at different places. Protons migrate in the resist matrix toward counter anions, attracted by the opposite electric charges. However, the details of proton migration are still unclear. In this study, we investigated proton quenching in poly(4-hydroxystyrene) films using base quenchers with different proton affinities. When the proton affinity of the base quencher was increased, the equimolecular proton adduct of the acid-sensitive dye was quenched without postexposure bake. Although the proton affinity is a gas-phase value, the quenching effect correlated well with the proton affinity.

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