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Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. In this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al 2 O 3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C 3 H 6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

Rechargeable Li-metal batteries have the potential to more than double the specific energy of the state-of-the-art rechargeable Li-ion batteries, making Li-metal batteries a prime candidate for next-generation high-energy battery technology 1-3 . However, current Li-metal batteries suffer from fast cycle degradation compared with their Li-ion battery counterparts 2,3 , preventing their practical adoption. A main contributor to capacity degradation is the disconnection of Li from the electrochemical circuit, forming isolated Li 4-8 . Calendar ageing studies have shown that resting in the charged state promotes further reaction of active Li with the surrounding electrolyte 9-12 . Here we discover that calendar ageing in the discharged state improves capacity retention through isolated Li recovery, which is in contrast with the well-known phenomenon of capacity degradation observed during the charged state calendar ageing. Inactive capacity recovery is verified through observation of Coulombic efficiency greater than 100% on both Li||Cu half-cells and anode-free cells using a hybrid continuous-resting cycling protocol and with titration gas chromatography. An operando optical setup further confirms excess isolated Li reactivation as the predominant contributor to the increased capacity recovery. These insights into a previously unknown pathway for capacity recovery through discharged state resting emphasize the marked impact of cycling strategies on Li-metal battery performance., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

The ever-greater complexity of modern electronic devices requires a larger chemical toolbox to support their fabrication. Here, we explore the use of 1-nitropropane as a small molecule inhibitor (SMI) for selective atomic layer deposition (ALD) on a combination of SiO 2 , Cu, CuO x , and Ru substrates. Results using water contact angle goniometry, Auger electron spectroscopy, and infrared spectroscopy show that 1-nitropropane selectively chemisorbs to form a high-quality inhibition layer on Cu and CuO x at an optimized temperature of 100 °C, but not on SiO 2 and Ru. When tested against Al 2 O 3 ALD, however, a single pulse of 1-nitropropane is insufficient to block deposition on the Cu surface. Thus, a new multistep process is developed for low-temperature Al 2 O 3 ALD that cycles through exposures of 1-nitropropane, an aluminum metalorganic precursor, and coreactants H 2 O and O 3 , allowing the SMI to be sequentially reapplied and etched. Four different Al ALD precursors were investigated: trimethylaluminum (TMA), triethylaluminum (TEA), tris(dimethylamido)aluminum (TDMAA), and dimethylaluminum isopropoxide (DMAI). The resulting area-selective ALD process enables up to 50 cycles of Al 2 O 3 ALD on Ru but not Cu, with 98.7% selectivity using TEA, and up to 70 cycles at 97.4% selectivity using DMAI. This work introduces a new class of SMI for selective ALD at lower temperatures, which could expand selective growth schemes to biological or organic substrates where temperature instability may be a concern.

Resistive random-access memory (RRAM) is a promising technology for data storage and neuromorphic computing; however, cycle-to-cycle and device-to-device variability limits its widespread adoption and high-volume manufacturability. Improving the structural accuracy of RRAM devices during fabrication can reduce these variabilities by minimizing the filamentary randomness within a device. Here, we studied area-selective atomic layer deposition (AS-ALD) of the HfO 2 dielectric for the fabrication of RRAM devices with higher reliability and accuracy. Without requiring photolithography, first we demonstrated ALD of HfO 2 patterns uniformly and selectively on Pt bottom electrodes for RRAM but not on the underlying SiO 2 /Si substrate. RRAM devices fabricated using AS-ALD showed significantly narrower operating voltage range (2.6 × improvement) and resistance states than control devices without AS-ALD, improving the overall reliability of RRAM. Irrespective of device size (1 × 1, 2 × 2, and 5 × 5 μm 2 ), we observed similar improvement, which is an inherent outcome of the AS-ALD technique. Our demonstration of AS-ALD for improved RRAM devices could further encourage the adoption of such techniques for other data storage technologies, including phase-change, magnetic, and ferroelectric RAM.

The composition of the solid electrolyte interphase (SEI) plays an important role in controlling Li-electrolyte reactions, but the underlying cause of SEI composition differences between electrolytes remains unclear. Many studies correlate SEI composition with the bulk solvation of Li ions in the electrolyte, but this correlation does not fully capture the interfacial phenomenon of SEI formation. Here, we provide a direct connection between SEI composition and Li-ion solvation by forming SEIs using polar substrates that modify interfacial solvation structures. We circumvent the deposition of Li metal by forming the SEI above Li + /Li redox potential. Using theory, we show that an increase in the probability density of anions near a polar substrate increases anion incorporation within the SEI, providing a direct correlation between interfacial solvation and SEI composition. Finally, we use this concept to form stable anion-rich SEIs, resulting in high performance lithium metal batteries.

At >95% Coulombic efficiencies, most of the capacity loss for Li metal anodes (LMAs) is through the formation and growth of the solid electrolyte interphase (SEI). However, the mechanism through which this happens remains unclear. One property of the SEI that directly affects its formation and growth is the SEI's solubility in the electrolyte. Here, we systematically quantify and compare the solubility of SEIs derived from ether-based electrolytes optimized for LMAs using in-operando electrochemical quartz crystal microbalance (EQCM). A correlation among solubility, passivity, and cyclability established in this work reveals that SEI dissolution is a major contributor to the differences in passivity and electrochemical performance among battery electrolytes. Together with our EQCM, X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (NMR) spectroscopy results, we show that solubility depends on not only the SEI's composition but also the properties of the electrolyte. This provides a crucial piece of information that could help minimize capacity loss due to SEI formation and growth during battery cycling and aging.

Improving Coulombic efficiency (CE) is key to the adoption of high energy density lithium metal batteries. Liquid electrolyte engineering has emerged as a promising strategy for improving the CE of lithium metal batteries, but its complexity renders the performance prediction and design of electrolytes challenging. Here, we develop machine learning (ML) models that assist and accelerate the design of high-performance electrolytes. Using the elemental composition of electrolytes as the features of our models, we apply linear regression, random forest, and bagging models to identify the critical features for predicting CE. Our models reveal that a reduction in the solvent oxygen content is critical for superior CE. We use the ML models to design electrolyte formulations with fluorine-free solvents that achieve a high CE of 99.70%. This work highlights the promise of data-driven approaches that can accelerate the design of high-performance electrolytes for lithium metal batteries.

Inorganic-rich solid-electrolyte interphases (SEIs) on Li metal anodes improve the electrochemical performance of Li metal batteries (LMBs). Therefore, a fundamental understanding of the roles played by essential inorganic compounds in SEIs is critical to realizing and developing high-performance LMBs. Among the prevalent SEI inorganic compounds observed for Li metal anodes, Li 3 N is often found in the SEIs of high-performance LMBs. Herein, we elucidate new features of Li 3 N by utilizing a suspension electrolyte design that contributes to the improved electrochemical performance of the Li metal anode. Through empirical and computational studies, we show that Li 3 N guides Li electrodeposition along its surface, creates a weakly solvating environment by decreasing Li + -solvent coordination, induces organic-poor SEI on the Li metal anode, and facilitates Li + transport in the electrolyte. Importantly, recognizing specific roles of SEI inorganics for Li metal anodes can serve as one of the rational guidelines to design and optimize SEIs through electrolyte engineering for LMBs.

Atomic layer deposition (ALD) is a technologically important method to grow thin films with high conformality and excellent thickness control from vapor phase precursors. The development of new thermal ALD processes can be limited by precursor reactivity and stability: reaction temperature and precursor design are among the few variables available to achieve higher reactivity in gas-phase reactions, unlike in solution synthesis, where the use of solvent and/or a catalyst can promote a desired reaction. To bridge this synthesis gap between vapor-phase and solution-phase, we demonstrate the use of an ultrathin coating layer of a vapor phase-compatible solvent─an ionic liquid (IL)─on our growth substrate to perform ALD of SnO. Successful SnO deposition is achieved using tin acetylacetonate and water, a process that otherwise would require a stronger counter-reactant such as ozone. The presence of the layer of IL allows a solvent-mediated reaction mechanism to take place on the growth substrate surface. We report a growth per cycle of 0.67 Å/cycle at a deposition temperature of 100 °C in an IL comprising 1-ethyl-3-methylimidazolium hydrogen sulfate. Characterization of the ALD films confirms the SnO film composition, and 1 H and 13 C NMR are used to probe the solvent-mediated ALD reaction, suggesting a solvent-mediated addition-elimination-type mechanism which breaks a C-C bond in acetylacetonate to form acetone and acetate. Density functional theory calculations show that the IL solvent is beneficial to the proposed solvent-mediated mechanism by lowering the C-C bond cleavage energetics of acetylacetonate compared to the vapor phase. A general class of ligand modification reactions for thermal ALD is thus introduced in this work.

The electrodeposition of low surface area lithium is critical to successful adoption of lithium metal batteries. Here, we discover the dependence of lithium metal morphology on electrical resistance of substrates, enabling us to design an alternative strategy for controlling lithium morphology and improving electrochemical performance. By modifying the current collector with atomic layer deposited conductive (ZnO, SnO 2 ) and resistive (Al 2 O 3 ) nanofilms, we show that conductive films promote the formation of high surface area lithium deposits, whereas highly resistive films promote the formation of lithium clusters of low surface area. We reveal an electrodeposition mechanism in which radial diffusion of electroactive species is promoted on resistive substrates, resulting in lateral growth of large (150 µm in diameter) planar lithium deposits. Using resistive substrates, similar lithium morphologies are formed in three distinct classes of electrolytes, resulting in up to ten-fold improvement in battery performance. Ultimately, we report anode-free pouch cells using the Al 2 O 3 -modified copper that maintain 60 % of their initial discharge capacity after 100 cycles, displaying the benefits of resistive substrates for controlling lithium electrodeposition., (© 2022. The Author(s).)

The adsorption of metalorganic and metal halide precursors on the SiO 2 surface plays an essential role in thin-film deposition processes such as atomic layer deposition (ALD). In the case of aluminum oxide (Al 2 O 3 ) films, the growth characteristics are influenced by the precursor structure, which controls both chemical reactivity and the geometrical constraints during deposition. In this work, a systematic study using a series of Al(CH 3 ) x Cl 3- x ( x = 0, 1, 2, and 3) and Al(C y H 2 y +1 ) 3 ( y = 1, 2, and 3) precursors is carried out using a combination of experimental spectroscopic techniques together with density functional theory calculations and Monte Carlo simulations to analyze differences across precursor molecules. Results show that reactivity and steric hindrance mutually influence the ALD surface reaction. The increase in the number of chlorine ligands in the precursor shifts the deposition temperature higher, an effect attributed to more favorable binding of the intermediate species due to higher Lewis acidity, while differences between precursors in film growth per cycle are shown to originate from variations in adsorption activation barriers and size-dependent saturation coverage. Comparison between the theoretical and experimental results indicates that the Al(C y H 2 y +1 ) 3 precursors are favored to undergo two ligand exchange reactions upon adsorption at the surface, whereas only a single Cl-ligand exchange reaction is energetically favorable upon adsorption by the AlCl 3 precursor. By pursuing the first-principles design of ALD precursors combined with experimental analysis of thin-film growth, this work enables a robust understanding of the effect of precursor chemistry on ALD processes.

The development of new resist materials is vital to fabrication techniques for next-generation microelectronics. Inorganic resists are promising candidates because they have higher etch resistance, are more impervious to pattern collapse, and are more absorbing of extreme ultraviolet (EUV) radiation than organic resists. However, there is limited understanding about how they behave under irradiation. In this work, a Hf-based hybrid thin film resist, known as "hafnicone", is deposited from the vapor-phase via molecular layer deposition (MLD), and its electron-beam and deep-ultraviolet (DUV)-induced patterning mechanism is explored. The hafnicone thin films are deposited at 100 °C by using the Hf precursor tetrakis(dimethylamido)hafnium(IV) and the organic precursor ethylene glycol. E-beam lithography, scanning electron microscopy, and profilometry are used to investigate the resist performance of hafnicone. With 3 M HCl as the developer, hafnicone behaves as a negative tone resist which exhibits a sensitivity of 400 μC/cm 2 and the ability to resolve 50 nm line widths. The resist is characterized via X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) to investigate the patterning mechanism, which is described in the context of classical nucleation theory. This study of hafnicone hybrid MLD demonstrates the ability for the bottom-up vapor deposition of inorganic resists to be utilized in advanced e-beam and DUV lithographic techniques.

Designing a stable solid-electrolyte interphase on a Li anode is imperative to developing reliable Li metal batteries. Herein, we report a suspension electrolyte design that modifies the Li + solvation environment in liquid electrolytes and creates inorganic-rich solid-electrolyte interphases on Li. Li 2 O nanoparticles suspended in liquid electrolytes were investigated as a proof of concept. Through theoretical and empirical analyses of Li 2 O suspension electrolytes, the roles played by Li 2 O in the liquid electrolyte and solid-electrolyte interphases of the Li anode are elucidated. Also, the suspension electrolyte design is applied in conventional and state-of-the-art high-performance electrolytes to demonstrate its applicability. Based on electrochemical analyses, improved Coulombic efficiency (up to ~99.7%), reduced Li nucleation overpotential, stabilized Li interphases and prolonged cycle life of anode-free cells (~70 cycles at 80% of initial capacity) were achieved with the suspension electrolytes. We expect this design principle and our findings to be expanded into developing electrolytes and solid-electrolyte interphases for Li metal batteries., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Achieving facile nucleation of noble metal films through atomic layer deposition (ALD) is extremely challenging. To this end, η 4 -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) 3 produces 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., (© 2022 Wiley-VCH GmbH.)

The conversion of CO 2 into fuels and chemicals is an attractive option for mitigating CO 2 emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C-C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C-C coupling on a supported Ru/TiO 2 catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO 2 hydrogenation behavior of the Ru surface, significantly enhancing the C 2+ production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems., Competing Interests: The authors declare no competing interest., (Copyright © 2022 the Author(s). Published by PNAS.)

Electronic and geometric interactions between active and support phases are critical in determining the activity of heterogeneous catalysts, but metal-support interactions are challenging to study. Here, it is demonstrated how the combination of the monolayer-controlled formation using atomic layer deposition (ALD) and colloidal nanocrystal synthesis methods leads to catalysts with sub-nanometer precision of active and support phases, thus allowing for the study of the metal-support interactions in detail. The use of this approach in developing a fundamental understanding of support effects in Pd-catalyzed methane combustion is demonstrated. Uniform Pd nanocrystals are deposited onto Al 2 O 3 /SiO 2 spherical supports prepared with control over morphology and Al 2 O 3 layer thicknesses ranging from sub-monolayer to a ≈4 nm thick uniform coating. Dramatic changes in catalytic activity depending on the coverage and structure of Al 2 O 3 situated at the Pd/Al 2 O 3 interface are observed, with even a single monolayer of alumina contributing an order of magnitude increase in reaction rate. By building the Pd/Al 2 O 3 interface up layer-by-layer and using uniform Pd nanocrystals, this work demonstrates the importance of controlled and tunable materials in determining metal-support interactions and catalyst activity., (© 2021 Wiley-VCH GmbH.)

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 SAM-protected 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 in-depth view of the influence of ALD processes on the SAM structure and the nucleation behavior of ALD on SAM-protected surfaces.

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO 2 to CO (CO 2 R), can also selectively catalyze thermal CO 2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO 2 R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO 2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments., (© 2021 Wiley-VCH GmbH.)

Coordination polymers deposited by hybrid molecular layer deposition (MLD) techniques are of interest as highly conformal, functional materials. Incorporation of a second metal into these coordination polymers can result in additional functionality or fine tuning of the materials properties. Here, we investigate the deposition of multi-metal coordination polymers using hybrid MLD of Zn-Al and Zn-Hf with ethylene glycol as the organic linker. It is found that facile transmetalation occurs for the Zn-Al films, which results in Al-rich films, but does not take place for the Zn-Hf films. Additionally, the Zn-Hf films are found to be more resilient to ambient conditions than the pure Zn-based coordination polymer.

Molecular layer deposition (MLD) is an attractive, vapor-phase deposition method for applications requiring ultrathin organic materials, such as photolithography, lithium batteries, and microelectronics. By using sequential self-limiting surface reactions, MLD offers excellent control over thickness and conformality, but there are also challenges such as a limited range of possible film compositions and long deposition times. In this study, we introduce a modified technique, termed ionic liquid assisted MLD (IL-MLD), that can overcome these barriers. By performing the surface reactions inside of an ultrathin layer of a compatible ionic liquid (IL), solvent effects are replicated inside a vacuum system, broadening the possible reactions to a much wider suite of chemistries. Using this strategy, the MLD of polyetherketoneketone, an industrially and research-relevant, high-performance thermoplastic, is reported. With this proof-of-concept, we demonstrate that IL-MLD can enable the synthesis of polymers via solvent- or catalyst-mediated reactions and establish an approach that may allow solution chemistries to be accessed in other vapor deposition techniques as well.

For years, many efforts in area selective atomic layer deposition (AS-ALD) have focused on trying to achieve high-quality self-assembled monolayers (SAMs), which have been shown by a number of studies to be effective for blocking deposition. Herein, we show that in some cases where a densely packed SAM is not formed, significant ALD inhibition may still be realized. The formation of octadecylphosphonic acid (ODPA) SAMs was evaluated on four metal substrates: Cu, Co, W, and Ru. The molecular orientation, chain packing, and relative surface coverage were evaluated using near-edge X-ray absorption fine structure (NEXAFS), Fourier transform infrared (FTIR) spectroscopy, and electrochemical impedance spectroscopy (EIS). ODPA SAMs formed on Co, Cu, and W showed strong angular dependence of the NEXAFS signal whereas ODPA on Ru did not, suggesting a disordered layer was formed on Ru. Additionally, EIS and FTIR spectroscopy confirmed that Co and Cu form densely packed, "crystal-like" SAMs whereas Ru and W form less dense monolayers, a surprising result since W-ODPA was previously shown to inhibit the ALD of ZnO and Al 2 O 3 best among all the substrates. This work suggests that multiple factors play a role in SAM-based AS-ALD, not just the SAM quality. Therefore, metrological averaging techniques (e.g., WCA and FTIR spectroscopy) commonly used for evaluating SAMs to predict their suitability for ALD inhibition should be supplemented by more atomically sensitive methods. Finally, it highlights important considerations for describing the mechanism of SAM-based selective ALD.

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/SiO 2 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 Al 2 O 3 ALD from trimethylaluminum and water. Investigation into interfacial effects at the interface between Cu and SiO 2 on Cu/SiO 2 patterns reveals both a gap at the SiO 2 edges and a pitch size-dependent nucleation delay of ZnO ALD on SiO 2 regions of multilayer DDT-coated patterns. In contrast, no impact on ZnO ALD is observed on the SiO 2 regions of monolayer DDT-coated patterns. We also show that these interfacial effects depend on the ALD chemistry. Whereas an Al 2 O 3 film grows on the TaN diffusion barrier of a DDT-treated Cu/SiO 2 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.

We introduce the synthesis of hybrid nanostructures comprised of ZnO nanocrystals (NCs) decorating nanosheets and nanowires (NWs) of MoS 2 prepared by atomic layer deposition (ALD). The concentration, size, and surface-to-volume ratio of the ZnO NCs can be systematically engineered by controlling both the number of ZnO ALD cycles and the properties of the MoS 2 substrates, which are prepared by sulfurizing ALD MoO 3 . Analysis of the chemical composition combined with electron microscopy and synchrotron X-ray techniques as a function of the number of ZnO ALD cycles, together with the results of quantum chemical calculations, help elucidate the ZnO growth mechanism and its dependence on the properties of the MoS 2 substrate. The defect density and grain size of MoS 2 nanosheets are controlled by the sulfurization temperature of ALD MoO 3 , and the ZnO NCs in turn nucleate selectively at defect sites on MoS 2 surface and enlarge with increasing ALD cycle numbers. At higher ALD cycle numbers, the coalescence of ZnO NCs contributes to an increase in areal coverage and NC size. Additionally, the geometry of the hybrid structures can be tuned by changing the dimensionality of the MoS 2 , by employing vertical NWs of MoS 2 as the substrate for ALD ZnO NCs, which leads to improvement of the relevant surface-to-volume ratio. Such materials are expected to find use in newly expanded applications, especially those such as sensors or photodevices based on a p-n heterojunction which relies on coupling transition-metal dichalcogenides with NCs.

Atomic layer deposition (ALD) is a powerful tool for achieving atomic level control in the deposition of thin films. However, several physical and chemical phenomena can occur which cause deviation from "ideal" film growth during ALD. Understanding the underlying mechanisms that cause these deviations is important to achieving even better control over the growth of the deposited material. Herein, we review several precursor chemisorption mechanisms and the effect of chemisorption on ALD growth. We then follow with a discussion on diffusion and its impact on film growth during ALD. Together, these two fundamental processes of chemisorption and diffusion underlie the majority of mechanisms which contribute to material growth during a given ALD process, and the recognition of their role allows for more rational design of ALD parameters.

Fine-tuning of the surface free energy (SFE) of a solid material facilitates its use in a wide range of applications requiring precise control of the ubiquitous presence of liquid on the surface. In this study, we found that the SFE of rare-earth oxide (REO) thin films deposited by atomic layer deposition (ALD) gradually decreased with increasing film thickness; however, these changes could not be understood by classical interaction models. Herein, the mechanism underlying the aforesaid decrease was systematically studied by measuring contact angles, surface potential, adhesion force, crystalline structures, chemical compositions, and morphologies of the REO films. A growth mode of the REO films was observed: layer-by-layer growth at the initial stage with an amorphous phase and subsequent crystalline island growth, accompanied by a change in the crystalline structure and orientation that affects the SFE. The portion of the surface crystalline facets terminated with (222) and (440) planes evolved with an increase in ALD cycles and film thickness, as an amorphous phase was transformed. Based on this information, we demonstrated an SFE-tuned liquid tweezer with selectivity to target liquid droplets. We believe that the results of this fundamental and practical study, with excellent selectivity to liquids, will have significant impacts on coating technology.

Rh-based catalysts have shown promise for the direct conversion of syngas to higher oxygenates. Although improvements in higher oxygenate yield have been achieved by combining Rh with metal oxide promoters, details of the structure of the promoted catalyst and the role of the promoter in enhancing catalytic performance are not well understood. In this work, we show that MoO 3 -promoted Rh nanoparticles form a novel catalyst structure in which Mo substitutes into the Rh surface, leading to both a 66-fold increase in turnover frequency and an enhancement in oxygenate yield. By applying a combination of atomically controlled synthesis, in situ characterization, and theoretical calculations, we gain an understanding of the promoter-Rh interactions that govern catalytic performance for MoO 3 -promoted Rh. We use atomic layer deposition to modify Rh nanoparticles with monolayer-precise amounts of MoO 3 , with a high degree of control over the structure of the catalyst. Through in situ X-ray absorption spectroscopy, we find that the atomic structure of the catalytic surface under reaction conditions consists of Mo-OH species substituted into the surface of the Rh nanoparticles. Using density functional theory calculations, we identify two roles of MoO 3 : first, the presence of Mo-OH in the catalyst surface enhances CO dissociation and also stabilizes a methanol synthesis pathway not present in the unpromoted catalyst; and second, hydrogen spillover from Mo-OH sites to adsorbed species on the Rh surface enhances hydrogenation rates of reaction intermediates.

The synthesis of an all-carbon backboned fluoropolymer using photoactivated molecular layer deposition (pMLD) is developed. pMLD is a vapor-phase, layer-by-layer, organic thin film synthesis method utilizing UV light, allowing for the creation of materials previously unavailable via thermal MLD. The carbon backbone is achieved by reacting an iodine-containing fluorocarbon monomer (1,4-diiodooctafluorobutane) and a diene monomer (1,5-hexadiene) under UV irradiation in a step-growth polymerization sequence. The polymerization occurs with a growth rate of 1.3 Å/cycle, forming a copolymer containing hydrocarbon and fluorocarbon segments. X-ray photoelectron spectroscopy (XPS) was used to confirm the formation of new carbon-carbon bonds and quantify the final film composition. In situ XPS thermal annealing experiments confirm the film stability up to 400 °C. The ability to pattern the fluoropolymer on a surface is demonstrated using a photomask, suggesting that these films could be incorporated into photolithographic processes. Together, these results demonstrate that pMLD can be used to synthesize carbon backboned films with photopatterning ability, expanding the available chemistries and potential applications of MLD polymers.

The electrochemical synthesis of ammonia from nitrogen under mild conditions using renewable electricity is an attractive alternative 1-4 to the energy-intensive Haber-Bosch process, which dominates industrial ammonia production. However, there are considerable scientific and technical challenges 5,6 facing the electrochemical alternative, and most experimental studies reported so far have achieved only low selectivities and conversions. The amount of ammonia produced is usually so small that it cannot be firmly attributed to electrochemical nitrogen fixation 7-9 rather than contamination from ammonia that is either present in air, human breath or ion-conducting membranes 9 , or generated from labile nitrogen-containing compounds (for example, nitrates, amines, nitrites and nitrogen oxides) that are typically present in the nitrogen gas stream 10 , in the atmosphere or even in the catalyst itself. Although these sources of experimental artefacts are beginning to be recognized and managed 11,12 , concerted efforts to develop effective electrochemical nitrogen reduction processes would benefit from benchmarking protocols for the reaction and from a standardized set of control experiments designed to identify and then eliminate or quantify the sources of contamination. Here we propose a rigorous procedure using 15 N 2 that enables us to reliably detect and quantify the electrochemical reduction of nitrogen to ammonia. We demonstrate experimentally the importance of various sources of contamination, and show how to remove labile nitrogen-containing compounds from the nitrogen gas as well as how to perform quantitative isotope measurements with cycling of 15 N 2 gas to reduce both contamination and the cost of isotope measurements. Following this protocol, we find that no ammonia is produced when using the most promising pure-metal catalysts for this reaction in aqueous media, and we successfully confirm and quantify ammonia synthesis using lithium electrodeposition in tetrahydrofuran 13 . The use of this rigorous protocol should help to prevent false positives from appearing in the literature, thus enabling the field to focus on viable pathways towards the practical electrochemical reduction of nitrogen to ammonia.

Methanol is a major fuel and chemical feedstock currently produced from syngas, a CO/CO 2 /H 2 mixture. Herein we identify formate binding strength as a key parameter limiting the activity and stability of known catalysts for methanol synthesis in the presence of CO 2 . We present a molybdenum phosphide catalyst for CO and CO 2 reduction to methanol, which through a weaker interaction with formate, can improve the activity and stability of methanol synthesis catalysts in a wide range of CO/CO 2 /H 2 feeds., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In situ characterization of catalysts gives direct insight into the working state of the material. Here, the design and performance characteristics of a universal in situ synchrotron-compatible X-ray diffraction cell capable of operation at high temperature and high pressure, 1373 K, and 35 bar, respectively, are reported. Its performance is demonstrated by characterizing a cobalt-based catalyst used in a prototypical high-pressure catalytic reaction, the Fischer-Tropsch synthesis, using X-ray diffraction. Cobalt nanoparticles supported on silica were studied in situ during Fischer-Tropsch catalysis using syngas, H 2 and CO, at 723 K and 20 bar. Post reaction, the Co nanoparticles were carburized at elevated pressure, demonstrating an increased rate of carburization compared with atmospheric studies.

Wide-bandgap perovskites are attractive top-cell materials for tandem photovoltaic applications. Comprehensive optical modeling is essential to minimize the optical losses of state-of-the-art perovskite/perovskite, perovskite/CIGS, and perovskite/silicon tandems. Such models require accurate optical constants of wide-bandgap perovskites. Here, we report optical constants determined with ellipsometry and spectrophotometry for two new wide-bandgap, cesium-formamidinium-based perovskites. We validate the optical constants by comparing simulated quantum efficiency and reflectance spectra with measured cell results for semi-transparent single-junction perovskite cells and find less than 0.3 mA/cm 2 error in the short-circuit current densities. Such simulations further reveal that reflection and parasitic absorption in the front ITO layer and electron contact are responsible for the biggest optical losses. We also show that the complex refractive index of methylammonium lead triiodide, the most common perovskite absorber for solar cells, can be used to generate approximate optical constants for an arbitrary wide-bandgap perovskite by translating the data along the wavelength axis. Finally, these optical constants are used to map the short-circuit current density of a textured two-terminal perovskite/silicon tandem solar cell as a function of the perovskite thickness and bandgap, providing a guide to nearly 20 mA/cm 2 matched current density with any perovskite bandgap between 1.56 and 1.68 eV.

In this study, molecular layer deposition (MLD) was used to deposit ultrathin films of methylene-bridged silicon oxycarbide (SiOC) using bis(trichlorosilyl)methane and water as precursors at room temperature. By utilizing bifunctional trichlorosilane precursors, films of SiOC can be deposited in a layer-by-layer manner, wherein a water co-reactant circumvents the need for plasma, high temperatures, or highly oxidizing precursors. In this manner, films could be grown without the degradation commonly seen in other SiOC deposition methods. Saturation behavior for both precursors was confirmed for the MLD process, and a constant growth rate of 0.5 ± 0.1 Å/cycle was determined. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy were used to verify the reaction between precursors and to gain insight into the final film composition. Unlike most MLD films, which grow polymers in a linear fashion, XPS analysis indicates that neighboring silanol groups within the films tend to condense, forming a highly cross-linked network structure, whereby, on average, two-thirds of silanol groups undergo a condensation reaction. Further indication of cross-linking is seen by XPS during in situ annealing, which shows exceptional temperature stability of the film up to 600 °C in vacuum, in contrast to linear SiOC films, which are known to degrade below this temperature. The films also exhibit high chemical stability against acids, bases, and solvents. A film density of 1.4 g/cm 3 was measured by X-ray reflectivity, while the dielectric constant and refractive index were determined to be 2.6 ± 0.3 and 1.6 ± 0.1, respectively, at a 633 nm wavelength. The low dielectric constant, high ease of deposition, and exceptional thermal and chemical stabilities of this MLD SiOC film suggest that it may have potential applications for electronic devices.

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O 2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO 2 , Al 2 O 3 , Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe 2 O 3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth., Competing Interests: The authors declare no competing financial interest.

The adsorption of the homotrifunctional 1,2,3-benzenetriol on Ge(100)-2 × 1 has been investigated by density functional theory calculations, Fourier transform infrared spectroscopy, and X-ray-photoelectron spectroscopy. The results show that the adsorption can occur through OH dissociation of all three hydroxyl groups, and that all three reaction pathways are kinetically and thermodynamically favorable. A coverage-dependent analysis shows that at low coverage, the molecule reacts to form a mix of trifold and dually bound adsorbates. As the coverage increases, the reactions are limited to dissociative adsorption through single and dual attachments. Calculations on the three possible dually bound configurations further reveals that the dissociative adsorption of the third hydroxyl group is limited by geometrical constraints to only two reaction channels. Finally, the proximity between OH-groups in the molecule favors intra- and intermolecular hydrogen bonding, which stabilizes singly and dually bound adsorbate configurations and limits the reactivity of the functional groups.

Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

A new generation of catalysts is needed to meet society's energy and resource requirements. Current catalyst synthesis does not fully achieve optimum control of composition, size, and structure. Atomic layer deposition (ALD) is an emerging technique that allows for synthesis of highly controlled catalysts in the form of films, nanoparticles, and single sites. The addition of ALD coatings can also be used to introduce promoters and improve the stability of traditional catalysts. Evolving research shows promise for applying ALD to understand catalytically active sites and create next-generation catalysts using advanced 3D nanostructures.

For atomic layer deposition (ALD) of doped, ternary, and quaternary materials achieved by combining multiple binary ALD processes, it is often difficult to correlate the material properties and growth characteristics with the process parameters due to a limited understanding of the underlying surface chemistry. In this work, in situ Fourier transform infrared (FTIR) spectroscopy was employed during ALD of zinc-oxide, tin-oxide, and zinc-tin-oxide (ZTO) with the precursors diethylzinc (DEZ), tetrakis(dimethylamino)tin (TDMASn), and H 2 O. The main aim was to investigate the molecular basis for the nucleation delay during ALD of ZTO, observed when ZnO ALD is carried out after SnO 2 ALD. Gas-phase FTIR spectroscopy showed that dimethylamine, the main reaction product of the SnO 2 ALD process, is released not only during SnO 2 ALD but also when depositing ZnO after SnO 2 , indicating incomplete removal of the ligands of the TDMASn precursor from the surface. Transmission FTIR spectroscopy performed during ALD on SiO 2 powder revealed that a significant fraction of the ligands persist during both SnO 2 and ZnO ALD. These observations provide experimental evidence for a recently proposed mechanism, based on theoretical calculations, suggesting that the elimination of precursor ligands is often not complete. In addition, it was found that the removal of precursor ligands by H 2 O exposure is even less effective when ZnO ALD is carried out after SnO 2 ALD, which likely causes the nucleation delay in ZnO ALD during the deposition of ZTO. The underlying mechanisms and the consequences of the incomplete elimination of precursor ligands are discussed.

Nanostructured core-shell Si-Ta 3 N 5 photoanodes were designed and synthesized to overcome charge transport limitations of Ta 3 N 5 for photoelectrochemical water splitting. The core-shell devices were fabricated by atomic layer deposition of amorphous Ta 2 O 5 onto nanostructured Si and subsequent nitridation to crystalline Ta 3 N 5 . Nanostructuring with a thin shell of Ta 3 N 5 results in a 10-fold improvement in photocurrent compared to a planar device of the same thickness. In examining thickness dependence of the Ta 3 N 5 shell from 10 to 70 nm, superior photocurrent and absorbed-photon-to-current efficiencies are obtained from the thinner Ta 3 N 5 shells, indicating minority carrier diffusion lengths on the order of tens of nanometers. The fabrication of a heterostructure based on a semiconducting, n-type Si core produced a tandem photoanode with a photocurrent onset shifted to lower potentials by 200 mV. CoTiO x and NiO x water oxidation cocatalysts were deposited onto the Si-Ta 3 N 5 to yield active photoanodes that with NiO x retained 50-60% of their maximum photocurrent after 24 h chronoamperometry experiments and are thus among the most stable Ta 3 N 5 photoanodes reported to date.

Area selective atomic layer deposition has the potential to significantly improve current fabrication approaches by introducing a bottom-up process in which robust and conformal thin films are selectively deposited onto patterned substrates. In this paper, we demonstrate selective deposition of dielectrics on metal/dielectric patterns by protecting metal surfaces using alkanethiol blocking layers. We examine alkanethiol self-assembled monolayers (SAMs) with two different chain lengths deposited both in vapor and in solution and show that in both systems, thiols have the ability to block surfaces against dielectric deposition. We show that thiol molecules can displace Cu oxide, opening possibilities for easier sample preparation. A vapor-deposited alkanethiol SAM is shown to be more effective than a solution-deposited SAM in blocking ALD, even after only 30 s of exposure. The vapor deposition also results in a much better thiol regeneration process and may facilitate deposition of the SAMs on porous or three-dimensional structures, allowing for the fabrication of next generation electronic devices.

Wide-band-gap mixed-halide CH3NH3PbI3-XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently, J-V performance. A perovskite solar cell converted from PbI2 with a dense bottom layer and porous top layer achieved higher device performance than those of analogue cells with a dense PbI2 top layer. This work demonstrates a facile way to control PbI2 film configuration and morphology simply by modification of spin-coating parameters without any additional chemical or thermal post-treatment.

Area-selective atomic layer deposition (AS-ALD) is attracting increasing interest because of its ability to enable both continued dimensional scaling and accurate pattern placement for next-generation nanoelectronics. Here we report a strategy for depositing material onto three-dimensional (3D) nanostructures with topographic selectivity using an ALD process with the aid of an ultrathin hydrophobic surface layer. Using ion implantation of fluorocarbons (CFx), a hydrophobic interfacial layer is formed, which in turn causes significant retardation of nucleation during ALD. We demonstrate the process for Pt ALD on both blanket and 2D patterned substrates. We extend the process to 3D structures, demonstrating that this method can achieve selective anisotropic deposition, selectively inhibiting Pt deposition on deactivated horizontal regions while ensuring that only vertical surfaces are decorated during ALD. The efficacy of the approach for metal oxide ALD also shows promise, though further optimization of the implantation conditions is required. The present work advances practical applications that require area-selective coating of surfaces in a variety of 3D nanostructures according to their topographical orientation.

Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.

Quantum dots (QDs) show promise as the absorber in nanostructured thin film solar cells, but achieving high device efficiencies requires surface treatments to minimize interfacial recombination. In this work, lead sulfide (PbS) QDs are grown on a mesoporous TiO2 film with a crystalline TiO2 surface, versus one coated with an amorphous TiO2 layer by atomic layer deposition (ALD). These mesoporous TiO2 films sensitized with PbS QDs are characterized by X-ray and electron diffraction, as well as X-ray absorption spectroscopy (XAS) in order to link XAS features with structural distortions in the PbS QDs. The XAS features are further analyzed with quantum simulations to probe the geometric and electronic structure of the PbS QD-TiO2 interface. We show that the anatase TiO2 surface structure induces PbS bond angle distortions, which increases the energy gap of the PbS QDs at the interface.

Nanoscale patterning of materials is widely used in a variety of device applications. Area selective atomic layer deposition (ALD) has shown promise for deposition of patterned structures with subnanometer thickness control. However, the current process is limited in its ability to achieve good selectivity for thicker films formed at higher number of ALD cycles. In this report, we demonstrate a strategy for achieving selective film deposition via a self-correcting process on patterned Cu/SiO2 substrates. We employ the intrinsically selective adsorption of octadecylphosphonic acid self-assembled monolayers on Cu over SiO2 surfaces to selectively create a resist layer only on Cu. ALD is then performed on the patterns to deposit a dielectric film. A mild etchant is subsequently used to selectively remove any residual dielectric film deposited on the Cu surface while leaving the dielectric film on SiO2 unaffected. The selectivity achieved after this treatment, measured by compositional analysis, is found to be 10 times greater than for conventional area selective ALD.

The power conversion efficiency of quantum-dot-sensitized solar cells (QDSSCs) hinges on interfacial charge transfer. Increasing quantum dot (QD) loading on the TiO2 anode has been proposed as a means to block recombination of electrons in the TiO2 to the hole transport material; however, it is not known whether a corresponding increase in QD-mediated recombination processes might lead to an overall higher rate of recombination. In this work, a 3-fold increase in PbS QD loading was achieved by the addition of an aqueous base to negatively charge the TiO2 surface during Pb cation deposition. Increased QD loading improved QDSSC device efficiencies through both increased light absorption and an overall reduction in recombination. Unexpectedly, we also found increased QD size had the detrimental effect of increasing recombination. Kinetic modeling of the effect of QD size on interfacial charge transfer processes provided qualitative agreement with the observed variation in recombination lifetimes. These results demonstrate a robust method of improving QD loading, identify the specific mechanisms by which increased QD deposition impacts device performance, and provide a framework for future efforts optimizing the device architecture of QDSSCs.

Nanostructured materials offer key advantages for third-generation photovoltaics, such as the ability to achieve high optical absorption together with enhanced charge carrier collection using low cost components. However, the extensive interfacial areas in nanostructured photovoltaic devices can cause high recombination rates and a high density of surface electronic states. In this feature article, we provide a brief review of some nanostructured photovoltaic technologies including dye-sensitized, quantum dot sensitized and colloidal quantum dot solar cells. We then introduce the technique of atomic layer deposition (ALD), which is a vapor phase deposition method using a sequence of self-limiting surface reaction steps to grow thin, uniform and conformal films. We discuss how ALD has established itself as a promising tool for addressing different aspects of nanostructured photovoltaics. Examples include the use of ALD to synthesize absorber materials for both quantum dot and plasmonic solar cells, to grow barrier layers for dye and quantum dot sensitized solar cells, and to infiltrate coatings into colloidal quantum dot solar cell to improve charge carrier mobilities as well as stability. We also provide an example of monolayer surface modification in which adsorbed ligand molecules on quantum dots are used to tune the band structure of colloidal quantum dot solar cells for improved charge collection. Finally, we comment on the present challenges and future outlook of the use of ALD for nanostructured photovoltaics.

Atomic layer deposition (ALD) is an attractive method to deposit uniform catalytic films onto high surface area electrodes. One interesting material for ALD synthesis is MnOx, a promising earth-abundant catalyst for the oxygen evolution reaction (OER). It has previously been shown that catalysts beginning as MnO synthesized using ALD on smooth glassy carbon (s-GC) electrodes and Mn2O3 obtained upon annealing MnO on s-GC are active OER catalysts. Here, we use ALD to deposit MnO on high surface area GC (HSA-GC) substrates, forming an active catalyst on a geometric surface area basis. We then characterize three types of catalysts, HSA-GC MnO, s-GC MnO, and annealed MnO (Mn2O3), using cyclic voltammetry (CV), scanning electron microscopy (SEM), and ex situ X-ray absorption spectroscopy (XAS). We show that under OER conditions, all three catalysts oxidize to similar surface states with a mixture of Mn(3+)/Mn(4+) and that MnOx surface area effects can account for the observed differences in the catalytic activity. We also demonstrate the need for a high surface area support for high OER activity on a geometric basis.

Adsorption of bifunctional organic molecules on semiconductor surfaces is important for surface modification; however, most bifunctional molecules previously studied have yielded mixtures of singly and dually tethered adsorbates. Here we report the adsorption of bifunctional 1,4-phenylene diisocyanide (PDI) on the Ge(100)-2 × 1 surface, in which singly bound adsorbates are selectively produced. As shown by polarized multiple internal reflection infrared spectroscopy experiments and density functional theory calculations, PDI adsorbates form a single C-dative bonding configuration through one of the isocyanide functionalities, retaining one unreacted isocyanide moiety per adsorbate. The angle of the molecular axis is ∼30° from the surface normal. The delocalized π* molecular orbital of the free molecule is also preserved upon adsorption. These results demonstrate the potential usefulness of isocyanide adsorbates as a means toward selective organic functionalization of semiconductor surfaces.