With progress in the semiconductor industry, transistor density on a single computer chip has increased dramatically. This has resulted in a continuous shrinkage of the minimum feature size printed through microlithography technology. Resist, as the pattern recording medium of such printing, has been extensively studied to achieve higher resolution, higher sensitivity and lower line edge roughness. For decades this has been realized through chemical amplification. With the feature size continuously shrinking and the energy of exposure source therefore exceeding the resist ionization threshold, the performance of conventional chemically amplified resists is approaching the limits. Novel high-performance chemically amplified resists or non-chemically amplified resists are urgently needed to meet the requirement of next generation lithography. In this work a negative tone chemically amplified resist system based on a novel method to control the catalytic chain reaction is presented. The method to control the catalytic chain reaction is demonstrated using two model polymer resists. This method is then applied to a fullerene-based molecular resist system and a combination of good industrial compatibility, high resolution and good sensitivity has been achieved in this resist. Through a chromatographic separation, another chemically amplified molecular resist was also developed with further improved performance. An alternative route to sensitivity improvement other than chemical amplification is then introduced and a family of fullerene-based metal containing materials is presented. Lithographic performance is compared between the fullerene-metal resists and their control materials without metal. Using an aberration corrected scanning transmission electron microscope, the distribution of metal in the resist film and its behavior during the lithography process is evaluated and discussed.