Direct patterning of thermoelectric metal chalcogenides can be challenging and is normally constrained to certain geometries and sizes. Here we report the synthesis, characterization, and direct writing of sub-10 nm wide bismuth sulfide (Bi2S3) using a single-source, spin-coatable, and electron-beam-sensitive bismuth(III) ethylxanthate precursor. In order to increase the intrinsically low carrier concentration of pristine Bi2S3, we developed a self-doping methodology in which sulfur vacancies are manipulated by tuning the temperature during vacuum annealing, to produce an electron-rich thermoelectric material. We report a room-temperature electrical conductivity of 6 S m–1 and a Seebeck coefficient of −21.41 μV K–1 for a directly patterned, substoichiometric Bi2S3 thin film. We expect that our demonstration of directly writable thermoelectric films, with further optimization of structure and morphology, can be useful for on-chip applications.
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