Low-temperature direct synthesis of high quality WS 2 thin films by plasma-enhanced atomic layer deposition for energy related applications

Seungmin Yeo, Dip K. Nandi, R. Rahul, Tae Hyun Kim, Bonggeun Shong, Yujin Jang, Jong Seong Bae, Jeong Woo Han, Soo Hyun Kim, Hyungjun Kim

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33 Citations (Scopus)


Tungsten disulfide (WS 2 ) thin films are grown on several types of substrates by plasma-enhanced atomic layer deposition (PEALD) technique using tungsten hexacarbonyl [W(CO) 6 ] and H 2 S plasma at a relatively low temperature of 350 °C. The method delivers polycrystalline WS 2 film with (0 0 2) preferential growth and the high quality films could be successfully grown with as low as 30 ALD cycles (corresponding to ∼3 nm of thickness). Density functional theory (DFT) calculation results reveal that both adsorption of W(CO) 6 and removal of CO ligand would be facilitated by usage of H 2 S plasma by generating the different defect sites on the basal plane. The typical self-limiting film growth (growth rate of ∼0.1 nm/cycle), characteristic of ideal ALD, is clearly observed with both the precursor and reactant pulsing time. X-ray diffractometry (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering spectrometry (RBS) are performed in details to study the as-grown WS 2 film on Si/SiO 2 substrate. The analysis results confirm the formation of polycrystalline film, with high purity and well-defined stoichiometry. The as-deposited WS 2 films are then explored as an electrode in the field of energy generation as well as energy storage. The films are uniformly and conformally grown on high surface-area 3 dimensional Ni-foam that show excellent activity towards hydrogen evolution reaction (HER). Significantly low overpotential of ∼280 mV is observed at a high operational current density of 100 mA cm −2 during HER in acid electrolyte. In addition, the as-grown films on stainless steel substrate also reveal the stable electrochemical performances in Na-ion battery as an anode with reasonably high areal capacity of ∼44.5 μAh cm −2 at the end of 50 charge-discharge cycles.

Original languageEnglish
Pages (from-to)596-605
Number of pages10
JournalApplied Surface Science
Publication statusPublished - 2018 Nov 30

Bibliographical note

Funding Information:
This work was supported by Mid-career Researcher Program through NRF grant funded by the MEST (2015R1A2A2A04004945), Korea Basic Science Institute under the R&D program (Project No. D38700) supervised by the Ministry of Science and ICT, Republic of Korea, a grant from the Advanced Technology Center (ATC) Program (10077265, Commercialization technology development of solid transition metal chloride precursor for semiconductor thin film) funded by the Ministry of Trade, Industry & Energy of the Republic of Korea, and the MOTIE (Ministry of Trade, Industry & Energy (#10080651) and KSRC (Korea Semiconductor Research Consortium) support program for the development of the future semiconductor device. The precursor used in this study was provided by UP Chemical Co. Ltd., Korea.

Publisher Copyright:
© 2018 Elsevier B.V.

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Condensed Matter Physics
  • Physics and Astronomy(all)
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films


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