Atomic layer deposition (ALD) provides a promising route for depositing uniform thin coatings of electrocatalysts useful in many technologies, including the splitting of water. For materials such as NiO x that readily form hydrous oxides, however, the smooth, compact films deposited by ALD may result in higher overpotentials due to low catalyst surface area compared to other deposition methods. Here, the use of ALD–NiO thin films as oxygen evolution reaction (OER) electrocatalysts is explored. Thin films of crystalline ALD–NiO are deposited and OER activity is tested using cyclic voltammetry (CV). Fe incorporated from the electrolyte can increase the activity of NiO, and it is shown that the turnover frequency (TOF) increases tenfold by going from an Fe‐poor to Fe‐rich KOH electrolyte. Applying a potential exfoliates the NiO, increasing the number of electrochemically accessible Ni sites. Interestingly, by X‐ray photoelectron spectroscopy (XPS) and CV, it is found that an Fe‐rich electrolyte reduces the amount of restructuring and oxidation is found. It is shown that a high surface area, high TOF catalyst may be created by using a two‐step process in which the sample is sequentially conditioned in Fe‐poor then Fe‐rich KOH. This work highlights the importance of pretreatment on catalytic activity for compact NiO films deposited by ALD.
Area-selective atomic layer deposition (AS-ALD) is a promising "bottom-up" alternative to current nanopatterning techniques. Self-assembled monolayers (SAM) have been successfully employed as deactivating agents to achieve AS-ALD. In this work, the formation of octadecylphosphonic acid (ODPA) SAMs is studied on four technologically important metal substrates: Cu, Co, W, and Ru. The SAM quality is shown to be dependent on temperature, solvent, and the nature of the substrate. The blocking ability of the ODPA-treated substrates is evaluated using ZnO and Al 2 O 3 model ALD processes. Spectroscopic analyses reveal that ODPA-assisted ALD blocking can be achieved to varying degrees of success on each metal. ODPAprotected W showed >90% selectivity after 32 nm ZnO and 8 nm Al 2 O 3 ALD, exhibiting the best blocking overall. For all substrates, ZnO ALD proved consistently easier to block than Al 2 O 3 , indicating the importance of precursor chemistry. Additionally, we show that the self-correcting process previously reported for Cu using an acetic acid etchant can be extended to Co. This process improves selective deposition of Al 2 O 3 on patterned Co/SiO 2 with feature sizes as small as 25 nm. Additional studies reveal that feature size and density affect the apparent selectivity in SAM-based AS-ALD, highlighting the importance of such considerations in future process developments.
The vapor-phase reaction of dodecanethiol (DDT) with copper oxide surfaces and the molecular level composition and structure of the resulting films were examined. Atomic force microscopy, cross-sectional transmission electron microscopy, and electron energy loss/electron dispersive spectroscopy reveal that, instead of forming self-assembled monolayers, DDT etches CuO surfaces to create ∼8 nm thick Cu-thiolate multilayers. These layers are composed of surprisingly well-ordered crystallites, oriented either parallel or perpendicular to the substrate surface. Pre-etching of the CuO to expose the underlaying copper metal is shown to prevent the formation of multilayers and instead allow for the formation of the expected monolayers. Water contact angle and Fourier transform infrared spectroscopy are further shown to be ineffective at distinguishing the multilayer and monolayer thiol films. Interestingly, the multilayer films are unstable in air, ripening into particles 20 μm wide and several hundred nanometers tall over the course of a week. Air exposure also leads to the slow oxidation of the sulfur and copper within the films at a rate similar to what has been seen before for DDT monolayers. As a result, the multilayers show no significant improvement over monolayers in the prevention of oxidation.
Monolayer and multilayer dodecanethiols (DDT) can be assembled onto a copper surface from the vapor phase depending on the initial oxidation state of the copper. The ability of the copper-bound dodecanethiolates to block atomic layer deposition (ALD) and the resulting behavior at the interfaces of Cu/SiO2 patterns during area-selective ALD (AS-ALD) are compared between mono- and multilayers. We show that multilayer DDT is ∼7 times more effective at blocking ZnO ALD from diethylzinc and water than is monolayer DDT. Conversely, monolayer DDT exhibits better performance than does multilayer DDT in blocking of Al2O3 ALD from trimethylaluminum and water. Investigation into interfacial effects at the interface between Cu and SiO2 on Cu/SiO2 patterns reveals both a gap at the SiO2 edges and a pitch size-dependent nucleation delay of ZnO ALD on SiO2 regions of multilayer DDT-coated patterns. In contrast, no impact on ZnO ALD is observed on the SiO2 regions of monolayer DDT-coated patterns. We also show that these interfacial effects depend on the ALD chemistry. Whereas an Al2O3 film grows on the TaN diffusion barrier of a DDT-treated Cu/SiO2 pattern, the ZnO film does not. These results indicate that the structure of the DDT layer and the ALD precursor chemistry both play an important role in achieving AS-ALD.
To enable area-selective atomic layer deposition (AS-ALD), self-assembled monolayers (SAMs) have been used as the surface inhibitor to block a variety of ALD processes. The integrity of the SAM throughout the ALD process is critical to AS-ALD. Despite the demonstrated effectiveness of inhibition by SAMs, nucleation during ALD eventually occurs on SAMprotected surfaces, but its impact on SAM structures is still not fully understood. In this study, we chose the octadecyltrichlorosilane (ODTS) SAM as a model system to investigate the evolution of crystallinity and structure of SAMs before and after ALD. The breakdown behavior of SAMs when exposed to ZnO and Al 2 O 3 ALD was systematically studied by combining synchrotron X-ray techniques and electron microscopy. We show that the crystallinity and structure of ODTS SAMs grown on Si substrates remain intact until a significant amount of material deposition takes place. In addition, the undesired ALD materials that grow on ODTS SAMs present contrasting morphologies: dispersed nanoparticles for ZnO while relatively continuous film for Al 2 O 3 . Lastly, substrate dependency was explored by comparing a Si substrate to single-crystal sapphire. Similar results in the evolution of SAM crystallinity and formation of ALD nuclei on top of SAM are observed in the ODTS−sapphire system. This study provides an indepth view of the influence of ALD processes on the SAM structure and the nucleation behavior of ALD on SAM-protected surfaces.
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