The acid diffusion in chemically amplified resists (a current standard resist for semiconductor device manufacturing) is a significant concern in the development of highly resolving resists. However, non-chemically amplified resists (non- CARs) are generally less sensitive to radiation than CARs due to lack of amplification mechanism. Recently, a negativetype non-CAR resist utilizing polarity change and radical crosslinking (a dual insolubilization resist) was proposed. In this study, an acid reactive compound was introduced into the organotin-containing dual insolubilization resists to improve their sensitivity. The synthesized resists were composed of triarylsulfonium cations as a polarity changer and radical generator, 2,2,2-trisubstituted acetophenone as a radical generator, triphenyl(4-vinylphenyl)stannane (TPSnSt) as an EUV absorption enhancer and a quencher, and 4-[(2,4-Dimethoxyphenyl)hydroxymethyl]phenylmethacrylate (ARMA) as a polymer-bound acid-reactive unit. By the incorporation of ARMA, the sensitivity to extreme ultraviolet (EUV) radiation was increased by 2.4 times (the exposure dose for insolubilization was decreased by approximately 60%). The sensitivity enhancement is considered to have been caused by the acid catalytic etherification of ARMA through dimerization and/or with 2,2,2-trisubstituted acetophenone units.
Chemically amplified resists have been used for the fabrication of semiconductor devices. With the miniaturization of circuits, the performance of chemically amplified resists approaches their limit due to the acid diffusion. The development of a novel platform without acid diffusion becomes important. In this study, we proposed a negative-type polymer resist used for extreme ultraviolet (EUV) and electron beam (EB) lithography. The proposed resist utilizes polarity change and radical crosslinking triggered by EUV/EB exposure. Polymers having triarylsulfonium cations and 2,2,2-trisubstitued acetophenone as side chains were designed for realizing the dual insolubilization property. 2,2,2- trisubstitued acetophenone was incorporated for the efficient radical generation on the polymer structure for the crosslinking. An onium salt was incorporated for the efficient use of thermalized electrons for the polarity change and the radical generation of the side chain. In addition, triphenyl-(4-vinyl-phenyl)-stannane (StTPSn) was incorporated into the resist polymer as the EUV/EB absorber to enhance sensitivity. The highly sensitive property of the designed polymers was demonstrated.
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