MoS2 Passivated Multilayer Graphene Membranes for Li-Ion Extraction From Seawater.

Abundant Li resources in the ocean are promising alternatives to refining ore, whose supplies are limited by the total amount and geopolitical imbalance of reserves in Earth's crust. Despite advances in Li+ extraction using porous membranes, they require screening other cations on a large scale due to the lack in precise control of pore size and inborn defects. Herein, MoS2 nanoflakes on a multilayer graphene membrane (MFs-on-MGM) that possess ion channels comprising i) van der Waals interlayer gaps for optimal Li+ extraction and ii) negatively charged vertical inlets for cation attraction, are reported. Ion transport measurements across the membrane reveal ≈6- and 13-fold higher selectivity for Li+ compared to Na+ and Mg2+ , respectively. Furthermore, continuous, stable Li+ extraction from seawater is demonstrated by integrating the membrane into a H2 and Cl2 evolution system, enabling more than 104 -fold decrease in the Na+ concentration and near-complete elimination of other cations.

Reduction of EUV resist damage by neutral beam etching.

Even though EUV lithography has the advantage of implenting a finer pattern compared to ArF immersion lithography due to the use of 13.5 nm instead of 193 nm as the wavelength of the light source, due to the low energy of EUV light source, EUV resist has a thinner thickness than conventional ArF resist. EUV resist having such a thin thickness is more vulnerable to radiation damage received during the etching because of its low etch resistance and also tends to have a problem of low etch selectivity. In this study, the radiation damage to EUV resist during etching of hardmask materials such as Si3N4, SiO2, etc using CF4gas was compared between neutral beam etching (NBE) and ion beam etching (IBE). When NBE was used, after the etching of 20 nm thick EUV resist, the line edge roughness increase and the critical dimension change of EUV resist were reduced by ∼1/3 and ∼1/2, respectively, compared to those by IBE. Also, at that EUV etch depth, the root mean square surface roughness value of EUV resist etched by NBE was ∼2/3 compared to that by IBE on the average. It was also confirmed that the etching selectivity between SiO2, Si3N4, etc and EUV resist was higher for NBE compared to IBE. The less damage to the EUV resist and the higher etch selectivity of materials such as Si3N4and SiO2over EUV resist for NBE compared to IBE are believed to be related to the no potential energy released by the neutralization of the ions during the etching by NBE.

Direct nanofluidic channels via hardening and wrinkling of thin polymer films.

In this study, we propose a rational route to create wrinkling patterns with individually controllable location and direction in thin polymer films. Optical and atomic force microscopy analysis confirmed the formation of straight wrinkles with a typical width of 1.51 to 1.55 µm and a height of 60 to 65 nm. Confocal fluorescence microscopy revealed that each wrinkle produces a continuous hollow channel that interconnects neighboring holes in the polymer film, demonstrating potential applications as nanoscale fluidic channel and reactor. Moreover, we propose a mechanism that considers the elastic deformation energy and interface energies as crucial parameters that govern the mechanical instabilities, which provides scaling relationships between the height, width, and thickness of the wrinkles. This offers additional opportunities for control over the size and aspect ratio of the wrinkles and channels.

Direct Observation of Carboxymethyl Cellulose and Styrene-Butadiene Rubber Binder Distribution in Practical Graphite Anodes for Li-Ion Batteries.

Despite the important role of carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) binders in graphite electrodes for Li-ion batteries, the direct analysis of these binders remains challenging, particularly at very low concentrations as in practical graphite anodes. In this paper, we report the systematic investigation of the physiochemical behavior of the CMC and SBR binders and direct observations of their distributions in practical graphite electrodes. The key to this unprecedented capability is combining the advantages of several analytic techniques, including laser-ablation laser-induced break-down spectroscopy, time of flight secondary ion mass spectrometry, and a surface and interfacial cutting analysis system. By correlating the vertical distribution with the adsorption behaviors of the CMC, our study reveals that the CMC migration toward the surface during the drying process depends on the degree of cross-linked binder-graphite network generation, which is determined by the surface property of graphite and CMC materials. The suggested analytical techniques enable the independent tracing of CMC and SBR, disclosing the different vertical distribution of SBR from that of the CMC binder in our practical graphite anodes. This achievement provides additional opportunity to analyze the correlation between the binder distribution and mechanical properties of the electrodes.

Electrical Double Layer of Supported Atomically Thin Materials.

The electrical double layer (EDL), consisting of two parallel layers of opposite charges, is foundational to many interfacial phenomena and unique in atomically thin materials. An important but unanswered question is how the "transparency" of atomically thin materials to their substrates influences the formation of the EDL. Here, we report that the EDL of graphene is directly affected by the surface energy of the underlying substrates. Cyclic voltammetry and electrochemical impedance spectroscopy measurements demonstrate that graphene on hydrophobic substrates exhibits an anomalously low EDL capacitance, much lower than what was previously measured for highly oriented pyrolytic graphite, suggesting disturbance of the EDL ("disordered EDL") formation due to the substrate-induced hydrophobicity to graphene. Similarly, electrostatic gating using EDL of graphene field-effect transistors shows much lower transconductance levels or even no gating for graphene on hydrophobic substrates, further supporting our hypothesis. Molecular dynamics simulations show that the EDL structure of graphene on a hydrophobic substrate is disordered, caused by the disruption of water dipole assemblies. Our study advances understanding of EDL in atomically thin limit.

Controlling electric potential to inhibit solid-electrolyte interphase formation on nanowire anodes for ultrafast lithium-ion batteries.

With increasing demand for high-capacity and rapidly rechargeable anodes, problems associated with unstable evolution of a solid-electrolyte interphase on the active anode surface become more detrimental. Here, we report the near fatigue-free, ultrafast, and high-power operations of lithium-ion battery anodes employing silicide nanowires anchored selectively to the inner surface of graphene-based micro-tubular conducting electrodes. This design electrically shields the electrolyte inside the electrode from an external potential load, eliminating the driving force that generates the solid-electrolyte interphase on the nanowire surface. Owing to this electric control, a solid-electrolyte interphase develops firmly on the outer surface of the graphene, while solid-electrolyte interphase-free nanowires enable fast electronic and ionic transport, as well as strain relaxation over 2000 cycles, with 84% capacity retention even at ultrafast cycling (>20C). Moreover, these anodes exhibit unprecedentedly high rate capabilities with capacity retention higher than 88% at 80C (vs. the capacity at 1C).

Anomalous Photovoltaic Response of Graphene-on-GaN Schottky Photodiodes.

Graphene has attracted great attention as an alternative to conventional metallic or transparent conducting electrodes. Despite its similarities with conventional electrodes, recent studies have shown that a single-atom layer of graphene possesses unique characteristics, such as a tunable work function and transparencies for electric potential, reactivity, and wetting. Nevertheless, a systematic analysis of graphene and semiconductor junction characteristics has not yet been carried out. Here, we report the photoresponse characteristics of graphene-on-GaN Schottky junction photodiodes (Gr-GaN SJPDs), showing a typical rectifying behavior and distinct photovoltaic and photoelectric responses. Following the initial abrupt response to UV illumination, the Gr-GaN SJPDs exhibited a distinct difference in photocarrier dynamics depending on the applied bias voltage, which is characterized by either a negative or positive change in photocurrent with time. We propose underlying mechanisms for the anomalous photocarrier dynamics based on the interplay between electrostatic molecular interactions over the one-atom-thick graphene and GaN junction and trapped photocarriers at the defect states in the GaN thin film.