Edge-enriched transition metal dichalcogenides,
such as WS
2
, are promising electrocatalysts for sustainable
production
of H
2
through the electrochemical hydrogen evolution reaction
(HER). The reliable and controlled growth of such edge-enriched electrocatalysts
at low temperatures has, however, remained elusive. In this work,
we demonstrate how plasma-enhanced atomic layer deposition (PEALD)
can be used as a new approach to nanoengineer and enhance the HER
performance of WS
2
by maximizing the density of reactive
edge sites at a low temperature of 300 °C. By altering the plasma
gas composition from H
2
S to H
2
+ H
2
S during PEALD, we could precisely control the morphology and composition
and, consequently, the edge-site density as well as chemistry in our
WS
2
films. The precise control over edge-site density was
verified by evaluating the number of exposed edge sites using electrochemical
copper underpotential depositions. Subsequently, we demonstrate the
HER performance of the edge-enriched WS
2
electrocatalyst,
and a clear correlation among plasma conditions, edge-site density,
and the HER performance is obtained. Additionally, using density functional
theory calculations we provide insights and explain how the addition
of H
2
to the H
2
S plasma impacts the PEALD growth
behavior and, consequently, the material properties, when compared
to only H
2
S plasma.
Adsorbed fragments can become reactive once sufficient numbers of molecules adsorb in their neighbourhood, which accelerates the crucial reaction steps in the deposition process.
To describe the atomic layer deposition (ALD) reactions of HfO2 from Hf(N(CH3)2)4 and H2O, a three-dimensional on-lattice kinetic Monte-Carlo model is developed. In this model, all atomistic reaction pathways in density functional theory (DFT) are implemented as reaction events on the lattice. This contains all steps, from the early stage of adsorption of each ALD precursor, kinetics of the surface protons, interaction between the remaining precursors (steric effect), influence of remaining fragments on adsorption sites (blocking), densification of each ALD precursor, migration of each ALD precursors, and cooperation between the remaining precursors to adsorb H2O (cooperative effect). The essential chemistry of the ALD reactions depends on the local environment at the surface. The coordination number and a neighbor list are used to implement the dependencies. The validity and necessity of the proposed reaction pathways are statistically established at the mesoscale. The formation of one monolayer of precursor fragments is shown at the end of the metal pulse. Adsorption and dissociation of the H2O precursor onto that layer is described, leading to the delivery of oxygen and protons to the surface during the H2O pulse. Through these processes, the remaining precursor fragments desorb from the surface, leaving the surface with bulk-like and OH-terminated HfO2, ready for the next cycle. The migration of the low coordinated remaining precursor fragments is also proposed. This process introduces a slow reordering motion (crawling) at the mesoscale, leading to the smooth and conformal thin film that is characteristic of ALD.
Type of publicationArticle (peer-reviewed)Link to publisher's version http://dx.doi.org/10.1021/cm303630eAccess to the full text of the published version may require a subscription.
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In this study, we investigated the diffusion of H-atoms to the subsurface and their further diffusion into the bulk of a Ni(111) crystal by means of density functional theory calculations in the context of thermal and plasma-assisted catalysis. The H-atoms at the surface can originate from the dissociative adsorption of H 2 or CH 4 molecules, determining the surface H-coverage. When a threshold H-coverage is passed, corresponding to 1.00 ML for the crystalline Ni(111) surface, the surface-bound H-atoms start to diffuse to the subsurface. A similar threshold coverage is observed for the interstitial H-coverage. Once the interstitial sites are filled up with a coverage above 1.00 ML of H, dissolution of interstitial H-atoms to the layer below the interstitial sites will be initiated. Hence, by applying a high pressure or inducing a reactive plasma and high temperature, increasing the H-flux to the surface, a large amount of hydrogen can diffuse in a crystalline metal like Ni and can be absorbed. The formation of metal hydride may modify the entire reaction kinetics of the system. Equivalently, the H-atoms in the bulk can easily go back to the surface and release a large amount of heat. In a plasma process, H-atoms are formed in the plasma, and therefore the energy barrier for dissociative adsorption is dismissed, thus allowing achievement of the threshold coverage without applying a high pressure as in a thermal process. As a result, depending on the crystal plane and type of metal, a large number of H-atoms can be dissolved (absorbed) in the metal catalyst, explaining the high efficiency of plasma-assisted catalytic reactions. Here, the mechanism of H-dissolution is established as a chemical identifier for the investigation of the reaction kinetics of a chemical process.
A method to obtain full mass-over-charge (m/z), time-resolved quadruple mass spectrometry (QMS) spectra of an atomic layer deposition (ALD) cycle is proposed. This method allows one to circumvent the limitations of traditional approaches for obtaining QMS information in ALD, as all m/z values can be simultaneously screened for the formation of reaction products in an efficient way. As a proof of concept this method was applied to the trimethylaluminum (TMA)-water process. This process has been studied extensively over the past decades. Besides the expected formation of CH 4 , the formation of gaseous HOAl(CH 3 ) 2 during the water pulse is observed, revealing a secondary reaction pathway for the water. The reaction energy and Gibbs free energy for different reactions are investigated computationally using density functional theory calculations, and confirm that the secondary reaction pathway is thermodynamically allowed for certain surface conditions.
ZrO2 is of very high interest for various applications in semiconductor industry especially as high-k dielectric in metal–insulator–metal (MIM) capacitor devices. Further improvement of deposition processes, of material properties, and of integration schemes is essential in order to meet the strict requirements of future devices. In this paper, the authors describe a solution to solve one of the key challenges by reducing the process time of the bottle neck high-k atomic layer deposition (ALD). The authors extensively optimized the most common ALD process used for the ZrO2 deposition (TEMAZ/O3) resulting now in a doubled growth rate compared to the published growth rates of maximum 1 Å/cycle. Chemical reactions explaining the origin of the high growth rate are proposed by theoretical process modelling. At the same time, the outstanding electrical properties of ZrO2 thin films could be preserved. Finally, the integration of the ZrO2 process in MIM capacitor devices with TiN electrodes was evaluated. Thereby, the known effect of TiN bottom electrode oxidation by the O3 process was analyzed and significantly reduced by different integration approaches including wet chemical treatments and ALD process variations. The resulting MIM capacitors show low leakage current and high polarity symmetry.
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