Metal Chalcogenides on Silicon Photocathodes for Efficient Water Splitting: A Mini Overview

In the photoelectrochemical (PEC) water splitting (WS) reactions, a photon is absorbed by a semiconductor, generating electron-hole pairs which are transferred across the semiconductor/electrolyte interface to reduce or oxidize water into oxygen or hydrogen. Catalytic junctions are commonly combined with semiconductor absorbers, providing electrochemically active sites for charge transfer across the interface and increasing the surface band bending to improve the PEC performance. In this review, we focus on transition metal (di)chalcogenide [TM(D)C] catalysts in conjunction with silicon photoelectrode as Earth-abundant materials systems. Surprisingly, there is a limited number of reports in Si/TM(D)C for PEC WS in the literature. We provide almost a complete survey on both layered TMDC and non-layered transition metal dichalcogenides (TMC) co-catalysts on Si photoelectrodes, mainly photocathodes. The mechanisms of the photovoltaic power conversion of silicon devices are summarized with emphasis on the exact role of catalysts. Diverse approaches to the improved PEC performance and the proposed synergetic functions of catalysts on the underlying Si are reviewed. Atomic layer deposition of TM(D)C materials as a new methodology for directly growing them and its implication for low-temperature growth on defect chemistry are featured. The multi-phase TM(D)C overlayers on Si and the operation principles are highlighted. Finally, challenges and directions regarding future research for achieving the theoretical PEC performance of Si-based photoelectrodes are provided

On the Atomic Layer Deposition into 2- versus 3- Dimensionally Ordered Nanoporous Media: Pore Size or Connectivity?

Atomic-layer deposition (ALD) is now being recognized as a powerful, general tool for modifying the surfaces of nanomaterials in applications for many energy conversion devices. However, ALD involves slow processes particularly when it is subjected to nanoporous media with high-aspect ratios. Predicting the exact experimental conditions of the desired reactions for coating inside deep pores by ALD is not available because of the lack of complete understanding of diffusion in nanoporous media. Here, we report a comparative study of the ALD coating onto two distinctive templates having nanopores, i.e., 2- and 3-dimensionally ordered media (DOM), of similar porosity and pore dimension. Self-supporting, crack-free templates were carefully prepared in centimeters for both 2- and 3-DOM and thus avoid any possible sources of uncontrollable diffusion of precursor gas molecules through unwanted microvoids and cracks. Comparison of the ALD coating profiles across the thickness of both templates reveals a fundamentally distinct coating mechanism. While a uniform growth zone develops along the pores of the 2-DOM (i.e., 1-D diffusion path), a gradual decrease in the deposition is observed in those of the 3-DOM (i.e., 3-D diffusion path) as ALD pulse time increases. This observation suggests an essential role of the pore connectivity, rather than individual pore sizes, in the gas diffusion dynamics inside nanoporous media. The present model can universally predict the ALD behaviors in nanoporous media even with different types of pore connectivity.11Nsciescopu

Direct patterning of metal oxides by hard templates and atomic layer deposition

We describe a procedure for one-step patterning of thin films of metal oxides (TiO2, Al2O3, and ZnO) using reusable hard templates and atomic layer deposition (ALD). This procedure, called contact area lithography (CAL), was inspired from an idea of pattern transfer at a contact area, which realises high patterning fidelity, and enables a universal approach for the nano/micrometre scale patterning of both inorganic and organic thin films, such as self-assembled monolayers [1]. Patterned hard silicon oxide was employed as a hard template and water-induced bridge formation is attributed to the origin of the observed adhesive contact force between the substrates and the templates during the pattern transfer. Non-contacted areas were served as growth sites for thin layers of various metal oxides by using ALD. CAL is a simple and universal method to form hard oxide thin film patterns without incorporation of resistive layers, and should have potential for applications in micro/nano electronics, optoelectronics, flexible electronics, biochips, and complex nanostructure fabrication.X1132sciescopu

Formation of yttria-stabilized zirconia nanotubes by atomic layer deposition toward efficient solid electrolytes

Abstract We describe a fabrication strategy for preparing yttria-stabilized zirconia nanotube (YSZ-NT) arrays embedded in porous alumina membranes by means of template-directed atomic layer deposition (ALD) technique. The individual YSZ-NTs have a high aspect-ratio of well over 120, about ~ 110 nm in diameter, and ~ 14 µm in length. Interfacing the tube arrays with porous Pt was also introduced on the basis of partial etching technique in order to construct Pt/YSZ-NTs/Pt membrane electrode assembly (MEA) structures. The resulting YSZ-NTs MEAs show a 7 mm in diameter with a roughness factor of ~ 2. Area specific resistance was measured up to 1.84 Ω cm2 at 400 °C using H2 as fuel

Mixed-Phase (2H and 1T) MoS₂ Catalyst for a Highly Efficient and Stable Si Photocathode

We describe the direct formation of mixed-phase (1T and 2H) MoS2 layers on Si as a photocathode via atomic layer deposition (ALD) for application in the photoelectrochemical (PEC) reduction of water to hydrogen. Without typical series-metal interfaces between Si and MoS2, our p-Si/SiOx/MoS2 photocathode showed efficient and stable operation in hydrogen evolution reactions (HERs). The resulting performance could be explained by spatially genuine device architectures in three dimensions (i.e., laterally homo and vertically heterojunction structures). The ALD-grown MoS2 overlayer with the mixed-phase 1T and 2H homojunction passivates light absorber and surface states and functions as a monolithic structure for effective charge transport within MoS2. It is also beneficial in the operation of p-i-n heterojunctions with inhomogeneous barrier heights due to the presence of mixed-phase cocatalysts. The effective barrier heights reached up to 0.8 eV with optimized MoS2 thicknesses, leading to a 670 mV photovoltage enhancement without employing buried Si p-n junctions. The fast-transient behaviors via light illumination show that the mixed-phase layered chalcogenides can serve as efficient cocatalysts by depinning the Fermi levels at the interfaces. A long-term operation of ~70 h was also demonstrated in a 0.5 M H2SO4 solution

Flexible 3D Electrodes of Free-Standing TiN Nanotube Arrays Grown by Atomic Layer Deposition with a Ti Interlayer as an Adhesion Promoter

Nanostructured electrodes and their flexible integrated systems have great potential for many applications, including electrochemical energy storage, electrocatalysis and solid-state memory devices, given their ability to improve faradaic reaction sites by large surface area. Although many processing techniques have been employed to fabricate nanostructured electrodes onto flexible substrates, these present limitations in terms of achieving flexible electrodes with high mechanical stability. In this study, the adhesion, mechanical properties and flexibility of TiN nanotube arrays on a Pt substrate were improved using a Ti interlayer. Highly ordered and well-aligned TiN nanotube arrays were fabricated on a Pt substrate using a template-assisted method with an anodic aluminum oxide (AAO) template and atomic layer deposition (ALD) system. We show that with the use of a Ti interlayer between the TiN nanotube arrays and Pt substrate, the TiN nanotube arrays could perfectly attach to the Pt substrate without delamination and faceted phenomena. Furthermore, the I-V curve measurements confirmed that the electric contact between the TiN nanotube arrays and substrate for use as an electrode was excellent, and its flexibility was also good for use in flexible electronic devices. Future efforts will be directed toward the fabrication of embedded electrodes in flexible plastic substrates by employing the concepts demonstrated in this study

Atomic-Layer Deposition into 2- versus 3‑Dimensionally Ordered Nanoporous Media: Pore Size or Connectivity?

Atomic-layer deposition (ALD) is now being recognized as a powerful, general tool for modifying the surfaces of nanomaterials in applications for many energy conversion devices. However, ALD involves slow processes particularly when it is subjected to nanoporous media with high-aspect ratios. Predicting the exact experimental conditions of the desired reactions for coating inside deep pores by ALD is not available because of the lack of complete understanding of diffusion in nanoporous media. Here, we report a comparative study of the ALD coating onto two distinctive templates having nanopores, i.e., 2- and 3-dimensionally ordered media (DOM), of similar porosity and pore dimension. Self-supporting, crack-free templates were carefully prepared in centimeters for both 2- and 3-DOM and thus avoid any possible sources of uncontrollable diffusion of precursor gas molecules through unwanted microvoids and cracks. Comparison of the ALD coating profiles across the thickness of both templates reveals a fundamentally distinct coating mechanism. While a uniform growth zone develops along the pores of the 2-DOM (i.e., 1-D diffusion path), a gradual decrease in the deposition is observed in those of the 3-DOM (i.e., 3-D diffusion path) as ALD pulse time increases. This observation suggests an essential role of the pore connectivity, rather than individual pore sizes, in the gas diffusion dynamics inside nanoporous media. The present model can universally predict the ALD behaviors in nanoporous media even with different types of pore connectivity

Initial Self-Ordering of Porous Anodic Alumina: Transition from Polydispersity to Monodispersity

Self-ordered porous anodic alumina (PAA) membranes have been widely employed as a scaffold for fabricating various nanomaterials and functional nanostructures with an excellent uniformity. The self-organization processes are only found in narrow experimental windows even in PAA, and their formation mechanisms have not been fully understood yet and might allow us to access a hint that generally extends into other material systems. Here, we revisit the self-organization process of PAA by experimentally observing its initial stage in great detail. Surface morphologies of PAA were carefully monitored which have been imprinted upon the first anodization in the solutions of oxalic acid around the inflection point in the current–time curves. The physical dimensions were analyzed by electron microscopy, and the degree of ordering was evaluated using the radial power spectral density method. We found that the inflection point reflects the occurrence of a uniform pore diameter as well as interpore distance which is crucial for the self-organization phenomena resulting from the minimization of surface free energy. The proposed model was further supported by electric field simulation near the inflection point

Edge-On MoS₂ Thin Films by Atomic Layer Deposition for Understanding the Interplay between the Active Area and Hydrogen Evolution Reaction

The edge sites of molybdenum disulfide (MoS₂) have been shown to be efficient electrocatalysts for the hydrogen evolution reaction (HER). To utilize these structures, two main strategies have been proposed. The first strategy is to use amorphous structures, which should be beneficial in maximizing the area of the edge-site moieties of MoS₂. However, these structures experience structural instability during HER. The other strategy is nanostructuring, in which, to enhance the resulting HER performance, the exposed surfaces of MoS₂ cannot be inert basal planes. Therefore, MoS₂ may need critical nanocrystallinity to produce the desired facets. Here, we first describe that when atomic layer deposition (ALD) is applied to layered materials such as MoS₂, MoS₂ exhibits the nonideal mode of ALD growth on planar surfaces. As a model system, the ALD of MoCl₅ and H₂S was studied. This nonideality does not allow for the conventional linear relationship between the growth thickness and the number of cycles. Instead, it provides the ability to control the relative ratios of the edge sites and basal planes of MoS₂ to the exposed surfaces. The number of edge sites produced was carefully characterized in terms of the geometric surface area and effective work function and was correlated to the HER performance, including Tafel slopes and exchange current densities. We also discussed how, as a result of the low growth temperature, the incorporation of chlorine impurities affected the electron doping and formation of mixed 2H and 1T phases. Remarkably, the resulting 1T phase was stable even upon thermal annealing at 400 °C. With the simple, planar MoS₂ films, we monitored the resulting catalytic performance, finding current densities of up to 20 mA cm^–2 at −0.3 V versus the reversible hydrogen electrode (RHE), a Tafel slope of 50–60 mV/decade, and an onset potential of 143 mV versus RHE