Low temperature phase-controlled synthesis of titanium di- and tri-sulfide by atomic layer deposition

Saravana Basuvalingam (Corresponding author), Yue Zhang, Matthew Bloodgood, Rasmus H. Godiksen, Alberto González Curto, Jan Philipp Hofmann, Marcel Verheijen, Erwin Kessels, Ageeth Bol (Corresponding author)

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19 Citations (Scopus)
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Phase-controlled synthesis of two-dimensional (2D) transition-metal chalcogenides (TMCs) at low temperatures with a precise thickness control has to date been rarely reported. Here, we report on a process for the phase-controlled synthesis of TiS2 (metallic) and TiS3 (semiconducting) nanolayers by atomic layer deposition (ALD) with precise thickness control. The phase control has been obtained by carefully tuning the deposition temperature and coreactant composition during ALD. In all cases, characteristic self-limiting ALD growth behavior with a growth per cycle (GPC) of 0.16 nm per cycle was observed. TiS2 was prepared at 100 °C using H2S gas as coreactant and was also observed using H2S plasma as a coreactant at growth temperatures between 150 and 200 °C. TiS3 was synthesized only at 100 °C using H2S plasma as the coreactant. The S2 species in the H2S plasma, as observed by optical emission spectroscopy, has been speculated to lead to the formation of the TiS3 phase at low temperatures. The control between the synthesis of TiS2 and TiS3 was elucidated by Raman spectroscopy, X-ray photoelectron spectroscopy, high-resolution electron microscopy, and Rutherford backscattering study. Electrical transport measurements showed the low resistive nature of ALD grown 2D-TiS2 (1T-phase). Postdeposition annealing of the TiS3 layers at 400 °C in a sulfur-rich atmosphere improved the crystallinity of the film and yielded photoluminescence at 0.9 eV, indicating the semiconducting (direct band gap) nature of TiS3. The current study opens up a new ALD-based synthesis route for controlled, scalable growth of transition-metal di- A nd tri-chalcogenides at low temperatures.

Original languageEnglish
Pages (from-to)9354-9362
Number of pages9
JournalChemistry of Materials
Issue number22
Early online date28 Oct 2019
Publication statusPublished - 26 Nov 2019


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