Thermodynamics, Adhesion, and Wetting at Li/Cu(-Oxide) Interfaces: Relevance for Anode-Free Lithium-Metal Batteries.

A rechargeable battery that employs a Li metal anode requires that Li be plated in a uniform fashion during charging. In "anode-free" configurations, this plating will occur on the surface of the Cu current collector (CC) during the initial cycle and in any subsequent cycle where the capacity of the cell is fully accessed. Experimental measurements have shown that the plating of Li on Cu can be inhomogeneous, which can lower the efficiency of plating and foster the formation of Li dendrites. The present study employs a combination of first-principles calculations and sessile drop experiments to characterize the thermodynamics and adhesive (i.e., wetting) properties of interfaces involving Li and other phases present on or near the CC. Interfaces between Li and Cu, Cu2O, and Li2O are considered. The calculations predict that both Cu and Cu2O surfaces are lithiophilic. However, sessile drop measurements reveal that Li wetting occurs readily only on pristine Cu. This apparent discrepancy is explained by the occurrence of a spontaneous conversion reaction, 2 Li + Cu2O → Li2O + 2 Cu, that generates Li2O as one of its products. Calculations and sessile drop measurements show that Li does not wet (newly formed) Li2O. Hence, Li that is deposited on a Cu CC where surface oxide species are present will encounter a compositionally heterogeneous substrate comprising lithiophillic (Cu) and lithiophobic (Li2O) regions. These initial heterogeneities have the potential to influence the longer-term behavior of the anode under cycling. In sum, the present study provides insights into the early stage processes associated with Li plating in anode-free batteries and describes mechanisms that contribute to inefficiencies in their operation.

Lamination of >21% Efficient Perovskite Solar Cells with Independent Process Control of Transport Layers and Interfaces.

Transport layer and interface optimization is critical for improving the performance and stability of perovskite solar cells (PSCs) but is restricted by the conventional fabrication approach of sequential layer deposition. While the bottom transport layer is processed with minimum constraints, the narrow thermal and chemical stability window of the halide perovskite (HP) layer severely restricts the choice of top transport layer and its processing conditions. To overcome these limitations, we demonstrate lamination of HPs─where two transport layer-perovskite half-stacks are independently processed and diffusion-bonded at the HP-HP interface─as an alternative fabrication strategy that enables self-encapsulated solar cells. Power conversion efficiencies (PCE) of >21% are realized using cells that incorporate a novel transport layer combination along with dual-interface passivation via self-assembled monolayers, both of which are uniquely enabled by the lamination approach. This is the highest reported PCE for any laminated PSC encapsulated between glass substrates. We further show that this approach expands the processing window beyond traditional fabrication processes and is adaptable for different transport layer compositions. The laminated PSCs retained >75% of their initial PCE after 1000 h of 1-sun illumination at 40 °C in air using an all-inorganic transport layer configuration without additional encapsulation. Furthermore, a laminated 1 cm2 device maintained a Voc of 1.16 V. The scalable lamination strategy in this study enables the implementation of new transport layers and interfacial engineering approaches for improving performance and stability.

Lithium Metal Anodes: Advancing our Mechanistic Understanding of Cycling Phenomena in Liquid and Solid Electrolytes.

Lithium metal anodes have the potential to be a disruptive technology for next-generation batteries with high energy densities, but their electrochemical performance is limited by a lack of fundamental understanding into the mechanistic origins that underpin their poor reversibility, morphological evolution (including dendrite growth), and interfacial instability. The goal of this perspective is to summarize the current state-of-the-art understanding of these phenomena, and highlight knowledge gaps where additional research is needed. The various stages of cycling are described sequentially, including nucleation, growth, open-circuit rest periods, and electrodissolution (stripping). A direct comparison of lessons learned from liquid and solid-state electrolyte systems is made throughout the discussion, providing cross-cutting insights between these research communities. Major themes of the discussion include electro-chemo-mechanical coupling, insights from in situ/operando analysis, and the interplay between experimental observations and computational modeling. Finally, a series of fundamental research questions are proposed to identify critical knowledge gaps and inform future research directions.

Subtractive Patterning of Nanoscale Thin Films Using Acid-Based Electrohydrodynamic-Jet Printing.

As an alternative to traditional photolithography, printing processes are widely explored for the patterning of customizable devices. However, to date, the majority of high-resolution printing processes for functional nanomaterials are additive in nature. To complement additive printing, there is a need for subtractive processes, where the printed ink results in material removal, rather than addition. In this study, a new subtractive patterning approach that uses electrohydrodynamic-jet (e-jet) printing of acid-based inks to etch nanoscale zinc oxide (ZnO) thin films deposited using atomic layer deposition (ALD) is introduced. By tuning the printing parameters, the depth and linewidth of the subtracted features can be tuned, with a minimum linewidth of 11 µm and a tunable channel depth with ≈5 nm resolution. Furthermore, by tuning the ink composition, the volatility and viscosity of the ink can be adjusted, resulting in variable spreading and dissolution dynamics at the solution/film interface. In the future, acid-based subtractive patterning using e-jet printing can be used for rapid prototyping or customizable manufacturing of functional devices on a range of substrates with nanoscale precision.

Atomic Layer Deposition of Cu Electrocatalysts on Gas Diffusion Electrodes for CO2 Reduction.

Electrochemical reduction of CO2 using Cu catalysts enables the synthesis of C2+ products including C2H4 and C2H5OH. In this study, Cu catalysts were fabricated using plasma-enhanced atomic layer deposition (PEALD), achieving conformal deposition of catalysts throughout 3-D gas diffusion electrode (GDE) substrates while maintaining tunable control of Cu nanoparticle size and areal loading. The electrochemical CO2 reduction at the Cu surface yielded a total Faradaic efficiency (FE) > 75% for C2+ products. Parasitic hydrogen evolution was minimized to a FE of ∼10%, and a selectivity of 42.2% FE for C2H4 was demonstrated. Compared to a line-of-sight physical vapor deposition method, PEALD Cu catalysts show significant suppression of C1 products compared to C2+, which is associated with improved control of catalyst morphology and conformality within the porous GDE substrate. Finally, PEALD Cu catalysts demonstrated a stable performance for 15 h with minimal reduction in the C2H4 production rate.

Visible-Light-Driven Photocatalysts for Self-Cleaning Transparent Surfaces.

Highly transparent photocatalytic self-cleaning surfaces capable of harvesting near-visible (365-430 nm) photons were synthesized and characterized. This helps to address a current research gap in self-cleaning surfaces, in which photocatalytic coatings that exhibit activity at wavelengths longer than ultraviolet (UV) generally have poor optical transparency, because of broadband scattering and the attenuation of visible light. In this work, the wavelength-dependent photocatalytic activity of Pt-modified TiO2 (Pt-TiO2) particles was characterized, which exhibited activity for wavelengths up to 430 nm. Pt-TiO2 nanoparticles were embedded in a mesoporous SiO2 sol-gel matrix, forming a superhydrophilic surface that allowed for water adsorption and formation of reactive oxide species upon illumination, resulting in the removal of organic surface contaminants. These self-cleaning surfaces only interact strongly with near-visible light (∼365-430 nm), as characterized by photocatalytic self-cleaning tests. Broadband visible transparency was preserved by generating a morphology composed of small clusters of Pt-TiO2 surrounded by a matrix of SiO2, which limited diffuse visible light scattering and attenuation. The wavelength-dependent self-cleaning rate by the films was quantified using stearic acid degradation under both monochromatic and AM1.5G spectral illumination. By varying the film morphology, the average transmittance relative to bare glass can be tuned from ∼93%-99%, and the self-cleaning rate can be adjusted by more than an order of magnitude. Overall, the ability to utilize photocatalysts with tunable visible light activity, while maintaining broadband transparency, can enable the use of photocatalytic self-cleaning surfaces for applications where UV illumination is limited, such as touchscreen displays.

Integrating Structural Colors with Additive Manufacturing Using Atomic Layer Deposition.

We demonstrate tunable structural color patterns that span the visible spectrum using atomic layer deposition (ALD). Asymmetric metal-dielectric-metal structures were sequentially deposited with nickel, zinc oxide, and a thin copper layer to form an optical cavity. The color response was precisely adjusted by tuning the zinc oxide (ZnO) thickness using ALD, which was consistent with model predictions. Owing to the conformal nature of ALD, this allows for uniform and tunable coloration of non-planar three-dimensional (3D) objects, as exemplified by adding color to 3D-printed parts produced by metal additive manufacturing. Proper choice of inorganic layered structures and materials allows the structural color to be stable at elevated temperatures, in contrast to traditional paints. To print multiple colors on a single sample, polymer inhibitors were patterned in a desired geometry using electrohydrodynamic jet (e-jet) printing, followed by area-selective ALD in the unpassivated regions. The ability to achieve 3D color printing, both at the micro- and macroscales, provides a new pathway to tune the optical and aesthetic properties during additive manufacturing.

Durable Liquid- and Solid-Repellent Elastomeric Coatings Infused with Partially Crosslinked Lubricants.

Surfaces that are resistant to both liquid fouling and solid fouling are critical for many industrial and biomedical applications. However, surfaces developed to address these challenges thus far have been generally susceptible to mechanical damage. Herein, we report the design and fabrication of robust solid- and liquid-repellent elastomeric coatings that incorporate partially crosslinked lubricating chains within a durable polymer matrix. In particular, we fabricated partially crosslinked omniphobic polyurethane (omni-PU) coatings that can repel a broad range of liquid and solid foulants. The fabricated coatings are an order of magnitude more resistant to cyclic abrasion than current state-of-the-art slippery surfaces. Further through the integration of classic wetting and tribology models, we introduce a new material design parameter (KAR) for abrasion-resistant polymeric coatings. This combination of mechanical durability and broad antifouling properties enables the implication of such coatings to a wide variety of industrial and medical settings, including biocompatible implants, underwater vehicles, and antifouling robotics.

Geometric Optimization of Bismuth Vanadate Core-Shell Nanowire Photoanodes using Atomic Layer Deposition.

In this study, systematic geometric tuning of core-shell nanowire (NW) architectures is used to decouple the contributions from light absorption, charge separation, and charge transfer kinetics in photoelectrochemical water oxidation. Core-shell-shell NW arrays were fabricated using a combination of hydrothermal synthesis of ZnO and atomic layer deposition (ALD) of SnO2 and BiVO4. The length and spacing of the NW scaffold, as well as the BiVO4 film thickness, were systematically tuned to optimize the photoelectrochemical performance. A photocurrent of 4.4 mA/cm2 was measured at 1.23 V vs RHE for sulfite oxidation and 4.0 mA/cm2 at 1.80 V vs RHE for water oxidation without a cocatalyst, which are the highest values reported to date for an ALD-deposited photoanode. Electromagnetic simulations demonstrate that spatial heterogeneity in light absorption along the core-shell NW length has a critical role in determining internal quantum efficiency. The mechanistic understandings in this study highlight the benefits of systematically optimizing electrode geometry at the nanoscale when designing photoelectrodes.

Molecular layer deposition of Li-ion conducting "Lithicone" solid electrolytes.

We demonstrate the fabrication of Li-containing ("lithicone") thin films prepared via molecular layer deposition (MLD) using lithium tert-butoxide and ethylene glycol. X-ray photoelectron spectroscopy reveals that the stoichiometry of the lithicone is Li1.5C2O1.8 (H omitted), with C-O-Li moieties present in the film. The bonding environment of lithicone is distinct from that of lithium carbonate or MLD alucone films. Electrochemical impedance spectroscopy measurements show that annealed lithicone films exhibit room temperature ionic conductivity of 3.6-5 × 10-8 S cm-1 with an activation energy of ∼0.6 eV. The lithicone MLD process provides a pathway to further develop hybrid inorganic-organic Li-ion conducting materials for future battery applications.

Area-Selective Atomic Layer Deposition Patterned by Electrohydrodynamic Jet Printing for Additive Manufacturing of Functional Materials and Devices.

There is an increasing interest in additive nanomanufacturing processes, which enable customizable patterning of functional materials and devices on a wide range of substrates. However, there are relatively few techniques with the ability to directly 3D print patterns of functional materials with sub-micron resolution. In this study, we demonstrate the use of additive electrohydrodynamic jet (e-jet) printing with an average line width of 312 nm, which acts as an inhibitor for area-selective atomic layer deposition (AS-ALD) of a range of metal oxides. We also demonstrate subtractive e-jet printing with solvent inks that dissolve polymer inhibitor layers in specific regions, which enables localized AS-ALD within those regions. The chemical selectivity and morphology of e-jet patterned polymers towards binary and ternary oxides of ZnO, Al2O3, and SnO2 were quantified using X-ray photoelectron spectroscopy, atomic force microscopy, and Auger electron spectroscopy. This approach enables patterning of functional oxide semiconductors, insulators, and transparent conducting oxides with tunable composition, Å-scale control of thickness, and sub-µm resolution in the x-y plane. Using a combination of additive and subtractive e-jet printing with AS-ALD, a thin-film transistor was fabricated using zinc-tin-oxide for the semiconductor channel and aluminum-doped zinc oxide as the source and drain electrical contacts. In the future, this technique can be used to print integrated electronics with sub-micron resolution on a variety of substrates.

Inkjet-defined site-selective (IDSS) growth for controllable production of in-plane and out-of-plane MoS2 device arrays.

Along with the increasing interest in MoS2 as a promising electronic material, there is also an increasing demand for nanofabrication technologies that are compatible with this material and other relevant layered materials. In addition, the development of scalable nanofabrication approaches capable of directly producing MoS2 device arrays is an imperative task to speed up the design and commercialize various functional MoS2-based devices. The desired fabrication methods need to meet two critical requirements. First, they should minimize the involvement of resist-based lithography and plasma etching processes, which introduce unremovable contaminations to MoS2 structures. Second, they should be able to produce MoS2 structures with in-plane or out-of-plane edges in a controlled way, which is key to increase the usability of MoS2 for various device applications. Here, we introduce an inkjet-defined site-selective (IDSS) method that meets these requirements. IDSS includes two main steps: (i) inkjet printing of microscale liquid droplets that define the designated sites for MoS2 growth, and (ii) site-selective growth of MoS2 at droplet-defined sites. Moreover, IDSS is capable of generating MoS2 with different structures. Specifically, an IDSS process using deionized (DI) water droplets mainly produces in-plane MoS2 features, whereas the processes using graphene ink droplets mainly produce out-of-plane MoS2 features rich in exposed edges. Using out-of-plane MoS2 structures, we have demonstrated the fabrication of miniaturized on-chip lithium ion batteries, which exhibit reversible lithiation/delithiation capacity. This IDSS method could be further expanded as a scalable and reliable nanomanufacturing method for generating miniaturized on-chip energy storage devices.

Enhanced Interfacial Toughness of Thermoplastic-Epoxy Interfaces Using ALD Surface Treatments.

Interfacial fracture and delamination of polymer interfaces can play a critical role in a wide range of applications, including fiber-reinforced composites, flexible electronics, and encapsulation layers for photovoltaics. However, owing to the low surface energy of many thermoplastics, adhesion to dissimilar material surfaces remains a critical challenge. In this work, we demonstrate that surface treatments using atomic layer deposition (ALD) on poly(methyl methacrylate) (PMMA) and fluorinated ethylene propylene (FEP) lead to significant increases in surface energy, without affecting the bulk mechanical response of the thermoplastic. After ALD film growth, the interfacial toughness of the PMMA-epoxy and FEP-epoxy interfaces increased by factors of up to 7 and 60, respectively. These results demonstrate the ability of ALD to engineer the adhesive properties of chemically inert surfaces. However, in the present case, the interfacial toughness was observed to decrease significantly with an increase in humidity. This was attributed to the phenomenon of stress-corrosion cracking associated with the reaction between Al2O3 and water and might have a significant implication for the design of these tailored interfaces.

Biotemplated Morpho Butterfly Wings for Tunable Structurally Colored Photocatalysts.

Morpho sulkowskyi butterfly wings contain naturally occurring hierarchical nanostructures that produce structural coloration. The high aspect ratio and surface area of these wings make them attractive nanostructured templates for applications in solar energy and photocatalysis. However, biomimetic approaches to replicate their complex structural features and integrate functional materials into their three-dimensional framework are highly limited in precision and scalability. Herein, a biotemplating approach is presented that precisely replicates Morpho nanostructures by depositing nanocrystalline ZnO coatings onto wings via low-temperature atomic layer deposition (ALD). This study demonstrates the ability to precisely tune the natural structural coloration while also integrating multifunctionality by imparting photocatalytic activity onto fully intact Morpho wings. Optical spectroscopy and finite-difference time-domain numerical modeling demonstrate that ALD ZnO coatings can rationally tune the structural coloration across the visible spectrum. These structurally colored photocatalysts exhibit an optimal coating thickness to maximize photocatalytic activity, which is attributed to trade-offs between light absorption and catalytic quantum yield with increasing coating thickness. These multifunctional photocatalysts present a new approach to integrating solar energy harvesting into visually attractive surfaces that can be integrated into building facades or other macroscopic structures to impart aesthetic appeal.

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition.

Superomniphobic surfaces display contact angles of θ* > 150° and low contact angle hysteresis with virtually all high and low surface tension liquids. The introduction of hierarchical scales of texture can increase the contact angles and decrease the contact angle hysteresis of superomniphobic surfaces by reducing the solid-liquid contact area. Thus far, it has not been possible to fabricate superomniphobic surfaces with three or more hierarchical scales of texture where the size, spacing, and angular orientation of features within each scale of texture can be independently varied and controlled. Here, we report a method for tunable control of geometry in hyperbranched ZnO nanowire (NW) structures, which in turn enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angles for a variety of liquids, which is supported by mathematical models. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles with water 172°/170°, hexadecane 166°/156°, octane 162°/145°, and heptane 160°/130°.

Dendrites and Pits: Untangling the Complex Behavior of Lithium Metal Anodes through Operando Video Microscopy.

Enabling ultra-high energy density rechargeable Li batteries would have widespread impact on society. However the critical challenges of Li metal anodes (most notably cycle life and safety) remain unsolved. This is attributed to the evolution of Li metal morphology during cycling, which leads to dendrite growth and surface pitting. Herein, we present a comprehensive understanding of the voltage variations observed during Li metal cycling, which is directly correlated to morphology evolution through the use of operando video microscopy. A custom-designed visualization cell was developed to enable operando synchronized observation of Li metal electrode morphology and electrochemical behavior during cycling. A mechanistic understanding of the complex behavior of these electrodes is gained through correlation with continuum-scale modeling, which provides insight into the dominant surface kinetics. This work provides a detailed explanation of (1) when dendrite nucleation occurs, (2) how those dendrites evolve as a function of time, (3) when surface pitting occurs during Li electrodissolution, (4) kinetic parameters that dictate overpotential as the electrode morphology evolves, and (5) how this understanding can be applied to evaluate electrode performance in a variety of electrolytes. The results provide detailed insight into the interplay between morphology and the dominant electrochemical processes occurring on the Li electrode surface through an improved understanding of changes in cell voltage, which represents a powerful new platform for analysis.

Macroporous p-GaP Photocathodes Prepared by Anodic Etching and Atomic Layer Deposition Doping.

P-type macroporous gallium phosphide (GaP) photoelectrodes have been prepared by anodic etching of an undoped, intrinsically n-type GaP(100) wafer and followed by drive-in doping with Zn from conformal ZnO films prepared by atomic layer deposition (ALD). Specifically, 30 nm ALD ZnO films were coated on GaP macroporous films and then annealed at T = 650 °C for various times to diffuse Zn in GaP. Under 100 mW cm(-2) white light illumination, the resulting Zn-doped macroporous GaP consistently exhibit strong cathodic photocurrent when measured in aqueous electrolyte containing methyl viologen. Wavelength-dependent photoresponse measurements of the Zn-doped macroporous GaP revealed enhanced collection efficiency at wavelengths longer than 460 nm, indicating that the ALD doping step rendered the entire material p-type and imparted the ability to sustain a strong internal electric field that preferentially drove photogenerated electrons to the GaP/electrolyte interface. Collectively, this work presents a doping strategy with a potentially high degree of controllability for high-aspect ratio III-V materials, where the ZnO ALD film is a practical dopant source for Zn.

Bioinspired Bifunctional Membrane for Efficient Clean Water Generation.

Solving the problems of water pollution and water shortage is an urgent need for the sustainable development of modern society. Different approaches, including distillation, filtration, and photocatalytic degradation, have been developed for the purification of contaminated water and the generation of clean water. In this study, we explored a new approach that uses solar light for both water purification and clean water generation. A bifunctional membrane consisting of a top layer of TiO2 nanoparticles (NPs), a middle layer of Au NPs, and a bottom layer of anodized aluminum oxide (AAO) was designed and fabricated through multiple filtration processes. Such a design enables both TiO2 NP-based photocatalytic function and Au NP-based solar-driven plasmonic evaporation. With the integration of these two functions into a single membrane, both the purification of contaminated water through photocatalytic degradation and the generation of clean water through evaporation were demonstrated using simulated solar illumination. Such a demonstration should also help open up a new strategy for maximizing solar energy conversion and utilization.

Quantifying Geometric Strain at the PbS QD-TiO2 Anode Interface and Its Effect on Electronic Structures.

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.

Core-Shell CdS-Cu2S Nanorod Array Solar Cells.

As an earth-abundant p-type semiconductor, copper sulfide (Cu2S) is an attractive material for application in photovoltaic devices. However, it suffers from a minority carrier diffusion length that is less than the length required for complete light absorption. Core-shell nanowires and nanorods have the potential to alleviate this difficulty because they decouple the length scales of light absorption and charge collection. To achieve this geometry using Cu2S, cation exchange was applied to an array of CdS nanorods to produce well-defined CdS-Cu2S core-shell nanorods. Previous work has demonstrated single-nanowire photovoltaic devices from this material system, but in this work, the cation exchange chemistry has been applied to nanorod arrays to produce ensemble-level devices with microscale sizes. The core-shell nanorod array devices show power conversion efficiencies of up to 3.8%. In addition, these devices are stable when measured in air after nearly one month of storage in a desiccator. These results are a first step in the development of large-area nanostructured Cu2S-based photovoltaics that can be processed from solution.