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

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Abstract

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
Volume31
Issue number22
Early online date28 Oct 2019
DOIs
Publication statusPublished - 26 Nov 2019

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Atomic layer deposition
Sulfides
Titanium
Thickness control
Chalcogenides
Plasmas
Transition metals
Temperature
Optical emission spectroscopy
Phase control
High resolution electron microscopy
Rutherford backscattering spectroscopy
Growth temperature
Sulfur
Raman spectroscopy
Photoluminescence
Energy gap
X ray photoelectron spectroscopy
Tuning
Gases

Cite this

@article{3cfa0327a2d34a4880d1ed0eb03d9a4a,
title = "Low temperature phase-controlled synthesis of titanium di- and tri-sulfide by atomic layer deposition",
abstract = "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.",
author = "Saravana Basuvalingam and Yue Zhang and Matthew Bloodgood and Godiksen, {Rasmus H.} and {Gonz{\'a}lez Curto}, Alberto and Hofmann, {Jan Philipp} and Marcel Verheijen and Erwin Kessels and Ageeth Bol",
year = "2019",
month = "11",
day = "26",
doi = "10.1021/acs.chemmater.9b02895",
language = "English",
volume = "31",
pages = "9354--9362",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Low temperature phase-controlled synthesis of titanium di- and tri-sulfide by atomic layer deposition

AU - Basuvalingam, Saravana

AU - Zhang, Yue

AU - Bloodgood, Matthew

AU - Godiksen, Rasmus H.

AU - González Curto, Alberto

AU - Hofmann, Jan Philipp

AU - Verheijen, Marcel

AU - Kessels, Erwin

AU - Bol, Ageeth

PY - 2019/11/26

Y1 - 2019/11/26

N2 - 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.

AB - 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.

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U2 - 10.1021/acs.chemmater.9b02895

DO - 10.1021/acs.chemmater.9b02895

M3 - Article

C2 - 31806923

AN - SCOPUS:85074938935

VL - 31

SP - 9354

EP - 9362

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 22

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