Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ALD”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Effect of pattern transfer process on roughness of block copolymer patterns from directed self-assembly

Block copolymer-directed self-assembly (DSA) remains promising for improving pattern quality and reducing the stochastic variations that challenge high numerical aperture extreme ultraviolet lithography. Equally critical is refining pattern transfer methods for accurately transferring the rectified DSA features to the underlying substrate. We compare two atomic layer deposition (ALD)-based techniques: sequential infiltration synthesis (SIS) and dry liftoff, applied to polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DSA patterns. Both methods utilize aluminum oxide hard masks, with one synthesized through infiltration into the PMMA domains and the other through conformal ALD coating. High-resolution scanning electron micrographs were analyzed to measure line edge, width, and placement roughness for both the line (PMMA) and space (PS) features. Although both methods yielded similar overall 3σ rms roughness, they differed significantly in the frequency-dependent power spectral density (PSD) profiles. SIS reduced line placement roughness at length scales associated with the polymer pitch, but increased space width roughness at low frequencies, whereas dry liftoff mimicked the frequency content of the original guiding pattern. This study underscores the importance of PSD evaluation in selecting optimal pattern transfer strategies for specific applications.

Block copolymers↗
DOE OSTI2018

Atomic Layer Deposition of Thin Films onto 3D Nanostructures: The Effect of Wall Tilt Angle and Aspect Ratio of Trenches

A theoretical model predicting the spatial profile of a film grown on walls by atomic layer deposition (ALD) is developed. The possible initial nonverticality of trench walls and the dynamic variation of the aspect ratio of the structure in the process of film growth in nanosized trenches are considered in this model. The dependence of the resulting film thickness and conformity on ALD process parameters is studied theoretically.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Atomic Layer Etching at the Tipping Point: An Overview

The ability to achieve near-atomic precision in etching different materials when transferring lithographically defined templates is a requirement of increasing importance for nanoscale structure fabrication in the semiconductor and related industries. The use of ultra-thin gate dielectrics, ultra thin channels, and sub-20 nm film thicknesses in field effect transistors and other devices requires near-atomic scale etching control and selectivity. There is an emerging consensus that as critical dimensions approach the sub-10 nm scale, the need for an etching method corresponding to Atomic Layer Deposition (ALD), i.e. Atomic Layer Etching (ALE), has become essential, and that the more than 30-year quest to complement/replace continuous directional plasma etching (PE) methods for critical applications by a sequence of individual, self-limited surface reaction steps has reached a crucial stage. A key advantage of this approach relative to continuous PE is that it enables optimization of the individual steps with regard to reactant adsorption, self-limited etching, selectivity relative to other materials, and damage of critical surface layers. In this overview we present basic approaches to ALE of materials, discuss similarities/crucial differences relative to thermal and plasma-enhanced ALD, and then review selected results on ALE of materials aimed at pattern transfer. Furthermore, the overview concludes with a discussion of opportunities and challenges ahead.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

TiO 2 Nanocoatings with Controllable Crystal Type and Nanoscale Topography on Zirconia Implants to Accelerate Bone Formation

In dentistry, zirconia implants have emerged as a promising alternative for replacing missing teeth due to their superior aesthetic performance and chemical stability. To improve the osseointegration of zirconia implants, modifying their surface with hierarchical micro/nanotopography and bioactive chemical composition are two effective ways. In this work, a microscale topography was prepared on a zirconia surface using hydrofluoric acid etching, and then a 50 nm TiO 2 nanocoating was deposited via atomic layer deposition (ALD). Subsequently, an annealing treatment was used to transform the TiO 2 from amorphous to anatase and simultaneously generate nanoscale topography. Various investigations into the coating surface morphology, topography, wettability, and chemical composition were carried out using scanning electron microscopy, white light interferometry, contact‐angle measurement, X‐ray diffraction, and X‐ray photoelectron spectroscopy. In addition, in vitro cytocompatibility and osteogenic potential performance of the coatings were evaluated by human bone marrow mesenchymal stem cells (hBMSCs), and in vivo osseointegration performance was assessed in a rat femoral condyle model. Moreover, the possible mechanism was also investigated. The deposition of TiO 2 film with/without annealing treatment did not alter the microscale roughness of the zirconia surface, whereas the nanotopography changed significantly after annealing. The in vitro studies revealed that the anatase TiO 2 coating with regular wavelike nanostructure could promote the adhesion and proliferation of osteoblasts and further improve the osteogenic potential in vitro and osseointegration in vivo. These positive effects may be caused by nanoscale topography via the canonical Wnt/ β ‐catenin pathway. The results suggest that using ALD in combination with annealing treatment to fabricate a nanotopographic TiO 2 coating is a promising way to improve the osteogenic properties of zirconia implants.

Li, Nan (ORCID:0000000255156737)↗
DOE OSTI2016

Designing optical metamaterial with hyperbolic dispersion based on Al:ZnO/ZnO nano-layered structure using Atomic Layer Deposition technique

In this study, nano-layered Al:ZnO/ZnO hyperbolic dispersion metamaterial with a large number of layers was fabricated using the atomic layer deposition (ALD) technique. Experimental dielectric functions for Al:ZnO/ZnO structures are obtained by an ellipsometry technique in the visible and near-infrared spectral ranges. The theoretical modeling of the Al:ZnO/ZnO dielectric permittivity is done using effective medium approximation. A method for analysis of spectroscopic ellipsometry data is demonstrated to extract the optical permittivity for this highly anisotropic nano-layered metamaterial. The results of the ellipsometry analysis show that Al:ZnO/ZnO structures with a 1:9 ALD cycle ratio exhibit hyperbolic dispersion transition change near 1.8 μm wavelength.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Enhanced radiative and thermal properties from surface encapsulation of InAs nanowires

In this work, photoluminescence (PL), quantum efficiency and carrier dynamics are investigated in indium arsenide (InAs) nanowires (NWs) with various surface treatments, including a molecular beam epitaxy (MBE)-grown semiconductor shell passivation, sulfur-passivation, alumina (Al 2 O 3 ) coating by atomic layer deposition (ALD) and polydimethylsiloxane (PDMS) spin-coating. The ALD-dielectric layer-coated InAs core-shell NWs show a maximum 13-fold increase in PL intensity. In contrast to the previous reports, this enhancement is found to be due to increased radiative rate from an enhanced Purcell factor, better thermal conductance and higher carrier injection within the NWs instead of improved surface quality. Numeric simulations confirm the experimentally observed increased radiative rate. Further improvements are suggested with even thicker capped InAs NWs. Carrier lifetime in surface-treated NWs is extended and shows long-term stability, critical for practical devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multiscale maps of Active Layer Depth for Teller site Mile Marker 27 and Kougarok Mile Marker 80, Seward Peninsula, AK

Remote sensing maps of active layer depth derived from Unmanned Areal System (UAS) data. The UAS datasets were stepwise scaled until matching the AVIRIS-NG (Airborne Visible / Infrared Imaging Spectrometer - Next Generation) and Sentinel-2 spatial resolutions. Using the field observed Active Layer Depth (ALD) measurement in combination with spectral and topographic predictors derivatives from DJI UAS imagery, we used a spatially explicit RF regression model to predict and map ALD across our study landscapes. This package includes maps for Next-Generation Ecosystem Experiment Arctic (NGEE Arctic)’s Teller Mile Marker (MM) 27, and Kougarok MM80 (aka Mile 80) watersheds. The field, map data, and metadata are provided as geoTIF and text (*.csv) formats. These datasets are provided in support of Hantson et al., 2024 (accepted) “Scaling Arctic landscape and permafrost features improves active layer depth modeling”

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Atomic layer deposition of cubic tin–calcium sulfide alloy films

Here, we deposit films of tin–calcium sulfide by atomic layer deposition (ALD) and demonstrate the metastability of this material. Rough and spiky films are obtained by using Sn and Ca precursors with different ligands, whereas compact and smooth films are obtained when the two metal sources share the same ligands. Compositional and quartz crystal microbalance results indicate that part of the underlaying SnS film is replaced and/or removed during the CaS ALD cycle during the ternary film deposition, possibly via a temperature-dependent cation exchange mechanism. The crystal structure transforms from orthorhombic to cubic as the calcium content increases. Furthermore, resistivity increases with calcium content in the alloy films, whereas optical band gap only depends weakly on Ca content. After annealing at 400 °C in an H 2 S environment, the cubic alloy film undergoes a phase transition into the orthorhombic phase and its resistivity also decreases. Both phenomena could be explained by phase separation of the metastable alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis and Understanding of Novel Catalysts

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supported metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron microcopy (STEM) to measure size and structure, energy dispersive X-ray spectroscopy (EDS) to measure atomic composition, X-ray absorption spectroscopy (XAS) to measure oxidation state and metal coordination, Fourier transform infrared spectroscopy (FTIR) to study adsorbed species, laser Raman spectroscopy to probe metal oxide promoters, and temperature programmed reaction/desorption to study the energetics of adsorption and desorption processes. We have studied our bimetallic catalysts for the selective cleavage of carbon-oxygen bonds, and we have studied the effects of adding metal oxide promoters to supported platinum and gold catalysts for water-gas shift (i.e., the production of hydrogen by reaction of carbon monoxide with water). We anticipate that the knowledge obtained from our studies will allow us to identify promising directions for new catalysts that show high activity, selectivity, and stability for important reactions, such as the conversion of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nucleation and Crystal Growth in the Formation of Hierarchical Three-Dimensional Nanoarchitecture

This project is to obtain fundamental understandings of the operation of the Ostwald-Lussac (OL) Law and the oriented attachment (OA) mechanism in nucleation and growth of TiO2 nanorods (NR) via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) process. Three-dimensional (3D) NW networks are a unique type of mesoporous architecture that offers extraordinary surface area density and superior transport properties of electrons, photons, and phonons. It is exceptionally promising for advancing the design and application of functional materials for photovoltaic devices, catalysts beds, hydrogen storage systems, sensors, and battery electrodes. Our group has developed the SPCVD technique by mimicking the mechanism of atomic layer deposition (ALD), which effectively decoupled the crystal growth from precursor concentration while retaining anisotropic 1D growth. For the first time, this technique realized a 3D NW architecture with ultrahigh density and achieved ~4-5 times enhancement on photo-conversion efficiency. Through the support of our current DOE award, we revealed the governing role of the OL Law in the nucleation stage of SPCVD. The formation of NR morphology in SPCVD was identified following the OA mechanism. We also discovered a unique vapor-phase Kirkendall effect in the evolution of tubular or core-shell NR structures. These understandings opened many new opportunities in designing 3D NW architectures with improved properties or new functionalities. Specifically, our accomplishments from this project include five aspects: (1) Observation of the Ostwald-Lussac Law in high-temperature ALD. (2) Observation of vapor-solid Kirkendall effect in ZnO-to-TiO2 nanostructure conversion. (3) Development of highly-efficient capillary photoelectrochemical (PEC) solar-fuel generation. (4) Development of efficient and stable electrochemical protections for black silicon PEC electrodes. (5) Development of doped polymers with tunable electrical properties. This project brings a new level of transformative knowledge on nucleation and crystal growth in the SPCVD NR growth processes. Specifically, quantification of the activation energy landscape guided by the OL law will allow us to establish a critical knowledge base of nucleation kinetics for SPCVD synthesis of NR branches on different material surfaces. Studying the OA kinetics will establish a transformative knowledge base to support this new crystal growth mechanism that can be applied to many functional material systems. This research will pave the road toward a capable and versatile synthesis technology for creating 3D hierarchical mesoscale structures.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Refractory Solar Selective Coatings

This three-year project worked towards developing high-performance selective receiver coatings for concentrated solar power (CSP) to meet the DOE SunShot 2020 goal of levelized cost of energy (LCOE) ≤6 ¢/kWhe. We exploited recent advances in photonic crystal fabrication and nanocomposite materials synthesis to manufacture coatings designed to withstand high operating temperatures in air (>800 °C) while maintaining a high solar absorptivity (≥95%) and low IR emissivity (≤10%). We engineered the selective receiver coatings at multiple length scales. In the 0.1-1 μm regime, the coating has a photonic crystal structure comprised of a periodic mesoporous array. This structure alters the photonic density of states to improve spectral selectivity while also mitigating thermal stress for improved lifetime. At the 1-10 nm scale, the coatings are composed of optically absorbing nanoparticles in a transparent matrix where the size, spacing, and composition of the nanoparticles are tailored to tune the optical properties for high visible absorption and low IR emittance - similar to a cermet, but with dramatically enhanced thermal stability. The photonic structure was fabricated by self-assembly from a nanoparticle suspension followed by infiltration using atomic layer deposition (ALD). The nanophase composite results by combining the ALD processes for a metal and a metal oxide.

14 SOLAR ENERGY↗
DOE OSTI2020

Enabling Efficiencies > 22.5% with Metal Oxide Passivating Contacts using Low-Cost Spatial Atomic Layer Deposition (Final Technical Report)

In this project, the University of Central Florida (UCF) worked to both increase module efficiency and reduce manufacturing cost by driving demonstrated lab-scale passivating contact technology using materials and processes compatible with high-volume manufacturing for crystalline silicon (c-Si) photovoltaic (PV) cells. Passivating contacts have garnered significant attention in recent years. They provide a means of suppressing contact recombination, a loss mechanism that limits the performance of industrially relevant cell architectures like Al back surface field (Al-BSF) cells and passivated emitter and rear cells (PERC). Most of the development of passivating contact technology has focused on the use of doped amorphous silicon or doped polysilicon contacts, but both suffer from parasitic optical absorption amongst other issues. Our team developed fully transparent hole-selective heterojunctions, deposited using atomic layer deposition (ALD), and showed how they could be incorporated into c-Si PV cells. The team conducted experiments to understand the process-structure-property relationship of hole-selective oxides, surface passivation oxide materials, and transparent conductive oxides deposited by ALD, and use that understanding to reduce contact recombination, contact resistivity, and parasitic optical absorption within c-Si PV cells. Before getting into the details of the report, we would like to note that COVID-19 has made it more challenging to conduct experimental research at UCF. UCF has a number of mandatory policies in place to ensure social distancing, testing, and contact tracing are all carried out in day-to-day operations. Despite these challenges, we worked diligently to make progress on this project in a manner that was as safe as possible. Over the course of the project, the UCF team and its collaborators have made the following discoveries and developments.

14 SOLAR ENERGY↗
DOE OSTI2021

Tuning Surface Stoichiometry of SOFC Electrodes at the Molecular and Nano-scale for Enhanced Performance and Durability

This project achieved the following objectives. Different cation segregation behaviors of different common SOFC cathodes, including La 0.6 Sr 0.4 Co0.2Fe 0.8 O 3-δ (LSCF), Sr 0.5 Sm 0.5 O 3-δ (SSC), and PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O5 +δ (PBSCF), were determined. We showed how oxygen partial pressure and gas impurities impact the stability of SOFC cathodes. We developed atomic layer deposition (ALD) coating techniques for electrodes and showed that by introducing different elements and different ALD oxidizers, electrode surface chemistry can be altered, resulting in enhanced oxygen reduction kinetics. In addition, we developed solution infiltration technique to enhance performance and durability of electrodes. Different infiltrates as well as different thermal treatment processes were screened to identify the optimal surface modification process that yields both low impedance and high durability. The modified cathode shows excellent stability and has a low area specific resistance (ASR) of only 0.2 Ωcm 2 at 600 °C after over 2000 hours of operation. Further, we developed ceramic anodes, SrFe(Co,Mo)O 3 (SFCM) and SrFe(Ni,Mo)O 3 (SFNM), and enhanced anode oxidation kinetics by solution infiltration or in situ catalyst exsolution from the ceramic anode surface. The modified anodes showed improved performance in full SOFCs, and the optimized anode modification shows high stability for over 400 hours at 550 °C. Moreover, the modified anode also demonstrates high durability in methane. This work provides fundamental understanding of electrode surface chemistry and demonstrates a simple, facile, cost-effective approach to enhance catalytic activity and durability of SOFC electrodes.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Selection and Characterization of Surrogate Material for Developing Zr Barrier Coatings for Uranium Nitride Particles

In support of UC 1-x N x fuel kernels (~ 800 micrometer diameter) development work ongoing at Oak Ridge national laboratory (ORNL), where the fuel kernels will be embedded inside a possible zirconium based matrix, Argonne National Laboratory (ANL) is contributing to help develop a robust metal diffusion barrier coating. Zirconium nitride (ZrN) and Zirconium oxide (ZrO2) were selected as possible diffusion barrier candidates, and the atomic layer deposition (ALD) has been chosen as a candidate technology to deposit the film. Development of such a barrier coating with the ALD process entails significant number of trials to study relevant parameters. Therefore, to prevent needless wastage, instead of coating directly over fuel kernels, a surrogate candidate with similar dimensions and physical properties were been selected and coated to develop the diffusion barrier coating.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

High-Temperature Linear Receiver Enabled by Multicomponent Aerogels

Concentrating solar thermal (CST) technology has significant potential mainly due to its dispatchability and low cost of storage. However, to compete with other sources, including utility-scale solar PV, its final cost (cents/kWh) still needs to be lowered. Cost reduction can be achieved by improving the system level efficiency of the CST plants through the deployment of advanced power cycles, which operate at high temperatures of ~700°C. However, optical, and thermal losses pose a major challenge to the efficiency of such CST systems. The overall aim of this project is to investigate and de-risk a linear solar receiver concept called an Aerogel Insulated Receiver (AIR) that generates high temperatures (up to 700°C) at a low solar concentration ratio (<100) and with a high collection efficiency (optical × receiver). Our prior work has demonstrated the thermal stability1 and optical and heat-insulating properties2,3 of transparent aerogel insulation at a one-inch scale. The focus of this work is on (1) co-optimization of the geometry of the aerogel tile and receiver enclosure to fit a standard parabolic collector (PTC), (2) scale-up of aerogels into 4-inch tiles while preserving key properties, (3) experimental measurement of receiver heat loss (W/m) in a >70-cm test stand and validation of anticipated receiver performance at high temperatures. Regarding (1), appropriate optical and thermal models for a parabolic trough receiver (PTR) are developed and validated. The geometry of the aerogels and the receiver enclosure are co-optimized to maximize the collection efficiency. The model predicts a 54% collection efficiency at 700°C for an AIR design based on flat aerogels. By combining the collection efficiency with the power block efficiency of supercritical CO 2 cycles, we predict >10% improvements in peak plant efficiency relative to existing line-focusing CST systems. The application of curved plasmonic aerogels is predicted to further increase the collection efficiency to 64%. Regarding (2), we demonstrate the successful development of 6-inch-long refractory aerogel tiles with optical, thermal, and stability characteristics consistent with our prior work. This scale-up requires a transition to a larger ALD station and modifying the ALD process variables such as exposure time and the number of precursor doses. Regarding (3), we design and develop an AIR test stand measuring 3 feet in length. Heat loss performance analysis is carried out using the test stand. The results indicate that aerogel insulation can significantly reduce receiver thermal losses at the high operating temperatures required for next-generation PTRs. The experimental results agree with the heat loss performance predicted by our receiver model. Lastly, we conducted preliminary failure mode and effects (FMEA) and techno-economic (TEA) analyses to identify failure mitigation strategies and commercial opportunities, respectively. Overall, this project identifies key opportunities and challenges in deploying aerogel insulating receivers in next-generation line-focusing CST technologies.

14 SOLAR ENERGY↗
DOE OSTI2022

Co-Free Cathode Materials and Their Novel Architectures

To enable cobalt-free LiNi 0.5 Mn 1.5 O 4 (LNMO) electrode and novel electrolyte formulation for use in next-generation Li-ion batteries (LIB) capable of high energy density, long cycle life and low cost, several methods were developed throughout this project. To enhance the performance of LNMO, Fe-doping on LNMO, laser treatment and atomic layer deposition (ALD) were adopted. Moreover, dry electrode method has successfully helped to fabricate ultra-high loading LNMO with stable performance. The improvement at anode side includes ALD-coating as well as pre-lithiation of graphite anode. In the novel electrolyte development, it was found that all-fluorinated electrolyte with appropriate additives can effectively extend both cycle and calendar life of LNMO full cells at practical loadings. Additional diagnosis of LNMO full cells showed that different types of carbon and porosity of separator play a critical role in the success of LNMO’s high voltage operation. The combined effort throughout the project pushed forward the understanding and commercialization of LNMO at practical level.

25 ENERGY STORAGE↗
DOE OSTI2026

Towards Spatial Control of Reaction Selectivity on Photocatalysts using Area Selective Atomic Layer Deposition on Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost H2; however, this approach is currently limited by solar-to-hydrogen (STH) conversion efficiencies in the sub-10% range. Z-scheme water splitting, in which H2 and O2 evolving particles are operated in separate compartments and electronically coupled by a soluble redox mediator, offers improvements in STH efficiency but introduces high rates of undesired side and back reactions. Nanoscopic oxide coatings (e.g., CrOx, and SiOx) have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as the particle can no longer facilitate both half reactions. In contrast to photodeposition, which may produce non-uniform overlayers due to the difficulty of controlling local electrochemical reactivity on the surface, area-selective atomic layer deposition (AS-ALD) can be used to deposit conformal ultrathin oxide coatings while preserving access to non-growth areas of a substrate surface. To develop this technique for Z-scheme photocatalysts, we performed AS-ALD of TiO2 on a dual site planar electrocatalyst based on interdigitated arrays of Pt and Au. Self-assembled monolayers of 1-octadecanethiol (ODT) were used to block growth on the Au array, resulting in a patterned surface in which only the Pt sites were encapsulated with TiO2. These electrocatalysts demonstrated localized reaction selectivity for hydrogen evolution reaction (HER) over the TiO2/Pt sites, while the uncoated Au sites retained activity towards Fe(II)/Fe(III) redox (FeRR). Under independent potential control, these microelectrodes showed that selectively deposited TiO2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared to uncoated control samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗