Nanostructures of metal sulfides are conventionally prepared via chemical techniques and patterned using self-assembly. This poses a considerable amount of challenge when arbitrary shapes and sizes of nanostructures are desired to be placed at precise locations. Here, we describe an alternative approach of nanoscale patterning of zinc sulfide (ZnS) directly using a spin-coatable and electron beam sensitive zinc butylxanthate resist without the lift-off or etching step. Time-resolved electron beam damage studies using micro-Raman and micro-FTIR spectroscopies suggest that exposure to a beam of electrons leads to quick disappearance of xanthate moieties most likely via the Chugaev elimination, and further increase of electron dose results in the appearance of ZnS, thereby making the exposed resist insoluble in organic solvents. Formation of ZnS nanocrystals was confirmed by high-resolution transmission electron microscopy and selected area electron diffraction. This property was exploited for the fabrication of ZnS lines as small as 6 nm and also enabled patterning of 10 nm dots with pitches as close as 22 nm. The ZnS patterns fabricated by this technique showed defect-induced photoluminescence related to sub-band-gap optical transitions. This method offers an easy way to generate an ensemble of functional ZnS nanostructures that can be arbitrarily patterned and placed in a precise way. Such an approach may enable programmable design of functional chalcogenide nanostructures.
Keywords: electron beam lithography; nanofabrication; photoluminescence; resists; single source precursors; xanthates; zinc sulfide.