A synthetic route toward hybrid MoS2‐based materials that combines the 2D bonding of MoS2with 3D networking of aliphatic carbon chains is devised, leading to a film with enhanced electrocatalytic activity. The hybrid inorganic–organic thin films are synthesized by combining atomic layer deposition (ALD) with molecular layer deposition (MLD) using the precursors molybdenum hexacarbonyl and 1,2‐ethanedithiol and characterized by in situ Fourier transform infrared spectroscopy, and the resultant material properties are probed by X‐ray photoelectron spectroscopy, Raman spectroscopy, and grazing incidence X‐ray diffraction. The process exhibits a growth rate of 1.3 Å per cycle, with an ALD/MLD temperature window of 155–175 °C. The hybrid films are moderately stable for about a week in ambient conditions, smooth (σRMS≈ 5 Å for films 60 Å thick) and uniform, with densities ranging from 2.2–2.5 g cm−3. The material is both optically transparent and catalytically active for the hydrogen evolution reaction (HER), with an overpotential (294 mV at −10 mA cm−2) superior to that of planar MoS2. The enhancement in catalytic activity is attributed to the incorporation of organic chains into MoS2, which induces a morphological change during electrochemical testing that increases surface area and yields high activity HER catalysts without the need for deliberate nanostructuring.
Wet chemical screening reveals the very high reactivity of Mo(NMe2)4with H2S for the low‐temperature synthesis of MoS2. This observation motivated an investigation of Mo(NMe2)4as a volatile precursor for the atomic layer deposition (ALD) of MoS2thin films. Herein we report that Mo(NMe2)4enables MoS2film growth at record low temperatures—as low as 60 °C. The as‐deposited films are amorphous but can be readily crystallized by annealing. Importantly, the low ALD growth temperature is compatible with photolithographic and lift‐off patterning for the straightforward fabrication of diverse device structures.
more » « less- NSF-PAR ID:
- 10035464
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 129
- Issue:
- 18
- ISSN:
- 0044-8249
- Format(s):
- Medium: X Size: p. 5073-5077
- Size(s):
- ["p. 5073-5077"]
- Sponsoring Org:
- National Science Foundation
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