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- 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
More Like this
-
more » « less
Abstract -
more » « less
Abstract Achieving facile nucleation of noble metal films through atomic layer deposition (ALD) is extremely challenging. To this end, η4‐2,3‐dimethylbutadiene ruthenium(0)tricarbonyl (Ru(DMBD)(CO)3), a zero‐valent complex, has recently been reported to achieve good nucleation by ALD at relatively low temperatures and mild reaction conditions. The authors study the growth mechanism of this precursor by in situ quartz‐crystal microbalance and quadrupole mass spectrometry during Ru ALD, complemented by ex situ film characterization and kinetic modeling. These studies reveal that Ru(DMBD)(CO)3produces high‐quality Ru films with excellent nucleation properties. This results in smooth, coalesced films even at low film thicknesses, all important traits for device applications. However, Ru deposition follows a kinetically limited decarbonylation reaction scheme, akin to typical chemical vapor deposition processes, with a strong dependence on both temperature and reaction timescale. The non‐self‐limiting nature of the kinetically driven mechanism presents both challenges for ALD implementation and opportunities for process tuning. By surveying reports of similar precursors, it is suggested that the findings can be generalized to the broader class of zero‐oxidation state carbonyl‐based precursors used in thermal ALD, with insight into the design of effective saturation studies.
-
more » « less
Abstract 2D materials have been of considerable interest as new materials for device applications. Non‐volatile resistive switching applications of MoS2and WS2have been previously demonstrated; however, these applications are dramatically limited by high temperatures and extended times needed for the large‐area synthesis of 2D materials on crystalline substrates. The experimental results demonstrate a one‐step sulfurization method to synthesize MoS2and WS2at 550
° C in 15 min on sapphire wafers. Furthermore, a large area transfer of the synthesized thin films to SiO2/Si substrates is achieved. Following this, MoS2and WS2memristors are fabricated that exhibit stable non‐volatile switching and a satisfactory large on/off current ratio (103–105) with good uniformity. Tuning the sulfurization parameters (temperature and metal precursor thickness) is found to be a straightforward and effective strategy to improve the performance of the memristors. The demonstration of large‐scale MoS2and WS2memristors with a one‐step low‐temperature sulfurization method with simple strategy to tuning can lead to potential applications such as flexible memory and neuromorphic computing. -
more » « less
Abstract It is reported that chemical vapor deposition (CVD) grown bilayer (BL) MoS2films are significantly more structurally stable in ambient air than CVD‐grown monolayer (ML) MoS2films that have been reported to structurally degrade in ambient air. The authors present atomic force microscopy (AFM) images of preheated and as‐grown ML and multilayer MoS2films after exposure to ambient air for periods of up to 2 years. The AFM images show that, in ambient air, preheated and as‐grown BL and thicker‐layer MoS2films do not exhibit the growth of dendrites that is characteristic of ML degradation. Dendrites are observed to stop at the ML‐BL boundary. Raman spectra of BLs exposed for up to 2 years are similar to those reported for as‐grown BLs. The greater stability of BLs and thicker layers are attributed to their indirect band gaps that suppress Förster resonance energy transfer processes that have been proposed to be responsible for ML degradation. The results show that BL and thicker‐layer transition metal dichalcogenides with indirect band gaps may be structurally stable in air and useful for ambient‐air applications.
-
more » « less
Abstract Area‐selective deposition (ASD) is a forefront nanopatterning technique gaining substantial attention in the semiconductor industry. While current research primarily addresses single‐material ASD, exploring multi‐material ASD is essential for mitigating complexity in advanced nanopatterning. This study describes molybdenum hexafluoride (MoF6)‐mediated fluorination/passivation of the hydroxylated SiO2(SiO2‒OH) at 250 °C as a new method to pacify nucleation during subsequent ZnO and TiO2atomic layer deposition (ALD). In contrast, Al2O3ALD is not passivated on the fluorinated SiO2(SiO2‒F). The study further shows that Mo ALD using MoF6and silane (1 wt% SiH4in Ar) selectively proceeds on hydrogen‐terminated Si (Si‒H), whereas SiO2‒OH becomes fluorine‐passivated without observable Mo deposition. This enables subsequent ZnO and TiO2ASD on Mo versus SiO2‒F, as confirmed by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). Proposed growth and inhibition mechanisms highlight the importance of the metal oxide precursor in achieving selectivity. Taken together, self‐aligned Mo/ZnO and Mo/TiO2nanoribbons are demonstrated on coplanar nanoscale Si‒H/SiO2‒OH patterns by sequentially integrating two individual ASD processes: 1) Mo ASD on Si‒H versus SiO2‒OH; and 2) ZnO or TiO2ASD on Mo versus SiO2‒F. This work highlights the potential for this approach in new ASD systems.
