Neil P. Dasgupta

Atomic layer deposition of platinum catalysts on nanowire surfaces for photoelectrochemical water reduction.

The photocathodic hydrogen evolution reaction (HER) from p-type Si nanowire (NW) arrays was evaluated using platinum deposited by atomic layer deposition (ALD) as a HER cocatalyst. ALD of Pt on the NW surface led to a highly conformal coating of nanoparticles with sizes ranging from 0.5 to 3 nm, allowing for precise control of the Pt loading in deep submonolayer quantities. The catalytic performance was measured using as little as 1 cycle of Pt ALD, which corresponded to a surface mass loading of ∼10 ng/cm(2). The quantitative exploration of the lower limits of Pt cocatalyst loading reported here, and its application to high-surface-area NW photoelectrodes, establish a general approach for minimizing the cost of precious-metal cocatalysts for efficient and affordable solar-to-fuel applications.

Atomic Layer Deposition of Metal Sulfide Materials

CONSPECTUS: The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application space, the benefits and challenges of novel ALD processes are emphasized and common trends are summarized. We conclude with a perspective on potential future directions for metal chalcogenide ALD as well as untapped opportunities. Finally, we consider challenges that must be addressed prior to implementing ALD metal sulfides into future device architectures.

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.

Atomic Layer Deposition of Lead Sulfide Quantum Dots on Nanowire Surfaces

Quantum dots provide unique advantages in the design of novel optoelectronic devices owing to the ability to tune their properties as a function of size. Here we demonstrate a new technique for fabrication of quantum dots during the nucleation stage of atomic layer deposition (ALD) of PbS. Islands with sub-10 nm diameters were observed during the initial ALD cycles by transmission electron microscopy, and in situ observations of the coalescence and sublimation behavior of these islands show the possibility of further modifying the size and density of dots by annealing. The ALD process can be used to cover high-aspect-ratio nanostructures, as demonstrated by the uniform coating of a Si nanowire array with a single layer of PbS quantum dots. Photoluminescence measurements on the quantum dot/nanowire composites show a blue shift when the number of ALD cycles is decreased, suggesting a route to fabricate unique three-dimensional nanostructured devices such as solar cells.

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.

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.

Bioinspired Multifunctional Paper-Based rGO Composites for Solar-Driven Clean Water Generation

Reusing polluted water through various decontamination techniques has appeared as one of the most practical approaches to address the global shortage of clean water. Rather than relying on single decontamination mechanism, herein we report the preparation and utilization of paper-based composites for multifunctional solar-driven clean water generation that is inspired by the multiple water purification approaches in biological systems. The reduced graphene oxide (rGO) sheets within such composites can efficiently remove organic contaminants through physical adsorption mechanism. Under solar irradiation, the floating rGO composites can instantly generate localized heating, which not only can directly generate clean water through distillation mechanism but also significantly enhance adsorption removal performance with the assistance of upward vapor flow. Such porous-structured paper-based composites allow for facile incorporation of photocatalysts to regenerate clean water out of contaminated water with combined adsorption, photodegradation, and interfacial heat-assisted distillation mechanisms. Within a homemade all-in-one water treatment device, the practical applicability of the composites for multifunctional clean water generation has been demonstrated.

Design of an atomic layer deposition reactor for hydrogen sulfide compatibility

A customized atomic layer deposition (ALD) reactor was designed with components compatible with hydrogen sulfide (H(2)S) chemistry. H(2)S is used as a reactant for the ALD of metal sulfides. The use of H(2)S in an ALD reactor requires special attention to safety issues due to its highly toxic, flammable, and corrosive nature. The reactor was designed with respect to materials compatibility of all wetted components with H(2)S. A customized safety interlock system was developed to shut down the system in the event of toxic gas leakage, power outage, loss of building ventilation or compressed air pressure. ALD of lead sulfide (PbS) and zinc sulfide (ZnS) were demonstrated with no chemical contamination or detectable release of H(2)S.

Dead lithium: mass transport effects on voltage, capacity, and failure of lithium metal anodes

Improvement of the performance of Li metal anodes is critical to enable high energy density rechargeable battery systems beyond Li-ion. However, a complete mechanistic understanding of electrode overpotential variations that occur during extended cycling of Li metal is lacking. Herein, we demonstrate that when using a Li metal electrode, the dynamic changes in voltage during extended cycles can be increasingly attributed to mass transport. It is shown that these mass transport effects arise as a result of dead Li accumulation at the Li metal electrode, which introduces a tortuous pathway for Li-ion transport. In Li–Li symmetric cells, mass transport effects cause the shape of the galvanostatic voltage response to change from “peaking” to “arcing”, along with an increase in total electrode overpotential. The continued accumulation of dead Li is also conclusively shown to directly cause capacity fade and rapid “failure” of Li–LCO full cells containing Li metal anodes. This work provides detailed insights into the coupled relationships between cycling, interphase morphology, mass transport and the overall cell performance. Furthermore, this work helps underscore the potential of Li–Li symmetric cells as a powerful analytical tool for understanding the effects of Li metal electrodes in full cell batteries.

Area-selective atomic layer deposition of lead sulfide: nanoscale patterning and DFT simulations.

Area-selective atomic layer deposition (ALD) of lead sulfide (PbS) was achieved on octadecyltrichlorosilane (ODTS)-patterned silicon substrates. We investigated the capability of ODTS self-assembled monolayers (SAMs) to deactivate the ALD PbS surface reactions as a function of dipping time in ODTS solution. The reaction mechanism was investigated using density functional theory (DFT), which showed that the initial ALD half-reaction is energetically unfavorable on a methyl-terminated SAM surface. Conventional photolithography was used to create oxide patterns on which ODTS SAMs were selectively grown. Consequently, PbS thin films were grown selectively only where ODTS was not present, whereas deposition was blocked in regions where ODTS was grown. The resulting fabricated patterns were characterized by scanning electron microscopy and Auger electron spectroscopy, which demonstrated that ALD PbS was well confined to defined patterns with high selectivity by ODTS SAMs. In addition, AFM lithography was employed to create nanoscale PbS patterns. Our results show that this method can be applied to various device-fabrication processes, presenting new opportunities for various nanofabrication schemes and manifesting the benefits of self-assembly.