| Abstract: | Silylated poly(4-hydroxystyrene)s and radical polymerized 4-tert-butyldimethylsilyloxystyrene (TBDMSOSt) were examined as electron beam resists. Commercial poly(4-hydroxystyrene) (PHS) with Mw = 1.69 × 104 and Mw/Mn = 5.41 was silylated with 1-(trimethylsilyl)imidazole and tert-butylchlorodimethylsilane. Both silylation reactions proceeded quantitatively to afford trimethylsilylated PHS with Mw = 3.93 × 104 and Mw/Mn = 4.91, and tert-butyldimethylsilylated PHS with Mw = 4.08 × 104 and Mw/Mn = 3.81. These 2 silyl ether polymers acted as a negative working resist to electron beam (EB) exposure. Sensitivity and contrast of tert- butyldimethylsilylated PHS were not affected by prebake temperature around its Tg of 97°C, while those of PHS were dependent on prebake temperature around its Tg of 160°C. At a prebake temperature of 125°C, the sensitivity parameter  and the contrast γ value were obtained as follows: 3.93 × 10−4 C cm−2 and 0.91 for PHS; 1.49 × 10−4 C cm−2 and 1.06 for trimethylsilylated PHS; 1.84 × 10−4 C cm−2 and 1.44 for tert-butyldimethylsilylated PHS. The silylation procedures obviously improved the sensitivity of PHS. TBDMSOSt was polymerized in bulk at 60°C with 2,2′-azobisisobutyronitrile (AIBN) as an initiator. The resultant poly(TBDMSOSt) possessed Mw = 3.01 × 105 and Mw/Mn = 1.92 and exhibited a sensitivity  of 1.60 × 10−5 C cm−2 and a γ value of 1.47. More than 10 times enhancement of sensitivity was observed compared with tert-butyldimethylsilylated PHS. Such a high sensitivity is probably due to the high molecular weight of the bulk polymerized material. Poly(TBDMSOSt) resolved an isolated line of 0.20 μm width and 0.5 μm line and space patterns. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1151–1157, 1998 |
