Chemical and Physical Drivers for Improvement in Permeance and Stability of Linker-Free Graphene Oxide Membranes.

Graphene oxide (GO) is a promising membrane material for chemical separations, including water treatment. However, GO has often required postsynthesis chemical modifications, such as linkers or intercalants, to improve either the permeability, performance, or mechanical integrity of GO membranes. In this work, we explore two different feedstocks of GO to investigate chemical and physical differences, where we observe up to a 100× discrepancy in the permeability-mass loading trade-off while maintaining nanofiltration capacity. GO membranes also show structural stability and chemical resilience to harsh pH conditions and bleach treatment. We probe GO and the resulting assembled membranes through a variety of characterization approaches, including a novel scanning-transmission-electron-microscopy-based visualization approach, to connect differences in sheet stacking and oxide functional groups to significant improvements in permeability and chemical stability.

Hybrid Approach to Fabricate Uniform and Active Molecular Junctions.

Molecules can serve as ultimate building blocks for extreme nanoscale devices. This requires their precise integration into functional heterojunctions, most commonly in the form of metal-molecule-metal architectures. Structural damage and nonuniformities caused by current fabrication techniques, however, limit their effective incorporation. Here, we present a hybrid fabrication approach enabling uniform and active molecular junctions. A template-stripping technique is developed to form electrodes with sub-nanometer smooth surfaces. Combined with dielectrophoretic trapping of colloidal nanorods, uniform sub-5 nm junctions are achieved. Uniquely, in our design, the top contact is mechanically free to move under an applied stimulus. Using this, we investigate the electromechanical tuning of the junction and its tunneling conduction. Here, the molecules help control sub-nanometer mechanical modulation, which is conventionally challenging due to instabilities caused by surface adhesive forces. Our versatile approach provides a platform to develop and study active molecular junctions for emerging applications in electronics, plasmonics, and electromechanical devices.

Highly Conductive and Permeable Nanocomposite Ultrafiltration Membranes Using Laser-Reduced Graphene Oxide.

Electrically conductive membranes are a promising avenue to reduce water treatment costs due to their ability to minimize the detrimental impact of fouling, to degrade contaminants, and to provide other additional benefits during filtration. Here, we demonstrate the facile and low-cost fabrication of electrically conductive membranes using laser-reduced graphene oxide (GO). In this method, GO is filtered onto a poly(ether sulfone) membrane support before being pyrolyzed via laser into a conductive film. Laser-reduced GO composite membranes are shown to be equally as permeable to water as the underlying membrane support and possess sheet resistances as low as 209 Ω/□. Application of the laser-reduced GO membranes is demonstrated through greater than 97% removal of a surrogate water contaminant, 25 µM methyl orange dye, with an 8 V applied potential. Furthermore, we show that laser-reduced GO membranes can be further tuned with the addition of p-phenylenediamine binding molecules to decrease the sheet resistance to 54 Ω/□.

Bayesian-Optimization-Assisted Laser Reduction of Poly(acrylonitrile) for Electrochemical Applications.

Laser reduction of polymers has recently been explored to rapidly and inexpensively synthesize high-quality graphitic and carbonaceous materials. However, in past work, laser-induced graphene has been restricted to semiaromatic polymers and graphene oxide; in particular, poly(acrylonitrile) (PAN) is claimed to be a polymer that cannot be laser-reduced successfully to form electrochemically active material. In this work, three strategies to surmount this barrier are employed: (1) thermal stabilization of PAN to increase its sp2 content for improved laser processability, (2) prelaser treatment microstructuring to reduce the effects of thermal stresses, and (3) Bayesian optimization to search the parameter space of laser processing to improve performance and discover morphologies. Based on these approaches, we successfully synthesize laser-reduced PAN with a low sheet resistance (6.5 Ω sq-1) in a single lasing step. The resulting materials are tested electrochemically, and their applicability as membrane electrodes for vanadium redox flow batteries is demonstrated. This work demonstrates electrodes that are processed in air, below 300 °C, which are cycled stably over 2 weeks at 40 mA cm-2, motivating further development of laser reduction of porous polymers for membrane electrode applications such as RFBs.

Conformal Encapsulation of Silver Nanowire Transparent Electrodes by Nanosized Reduced Graphene Oxide Leading to Improved All-Round Stability.

Solution-processed silver nanowire (AgNW) networks are promising as next-generation transparent conductive electrodes due to their excellent optoelectronic properties, mechanical flexibility, as well as low material and processing costs. However, AgNWs are prone to thermally induced fragmentation and chemical degradation, necessitating a conformal protective coating typically achieved by low-throughput methods such as sputtering or atomic layer deposition. Herein, we report a facile all-solution-based approach to synthesize a conformally coated AgNW network by nanosized reduced graphene oxide R(nGO). In this method, probe ultrasonication is used to obtain nanosized GO, which is coated on AgNWs by a layer-by-layer approach and then chemically treated to form R(nGO)/AgNW. We show that our transparent electrode has excellent transmittance (85-92%) and sheet resistance (17.5 Ω/sq), combined with outstanding thermal and electrothermal stability, thanks to the conformal nature of the R(nGO) film, and demonstrate its use as a transparent heater with a high maximum temperature. This, in conjunction with improved long-term chemical and mechanical bending stability of R(nGO)/AgNW, indicates that our newly developed process represents an effective and low-cost strategy to improve the overall operational resilience of metal nanowire-based transparent conductive electrodes.

Oxynitride-Encapsulated Silver Nanowire Transparent Electrode with Enhanced Thermal, Electrical, and Chemical Stability.

Silver nanowire (AgNW) networks have been explored as a promising technology for transparent electrodes due to their solution-processability, low-cost implementation, and excellent trade-off between sheet resistance and transparency. However, their large-scale implementation in applications such as solar cells, transparent heaters, and display applications has been hindered by their poor thermal, electrical, and chemical stability. In this work, we present reactive sputtering as a method for fast deposition of metal oxynitrides as an encapsulant layer on AgNWs. Because O2 cannot be used as a reactive gas in the presence of oxidation-sensitive materials such as Ag, N2 is used under moderate sputtering base pressures to leverage residual H2O on the sample and chamber to deposit Al, Ti, and Zr oxynitrides (AlOxNy, TiOxNy, and ZrOxNy) on Ag nanowires on glass and polymer substrates. All encapsulants improve AgNW networks' electrical, thermal, and chemical stability. In particular, AlOxNy-encapsulated networks present exceptional chemical stability (negligible increase in resistance over 7 days at 80% relative humidity and 80 °C) and transparency (96% for 20 nm films on AgNWs), while TiOxNy demonstrates exceptional thermal and electrical stability (stability up to over temperatures 100 °C more than that of bare AgNW networks, with a maximum areal power density of 1.72 W/cm2, and no resistance divergence at up to 20 V), and ZrOxNy presents intermediate properties in all metrics. In summary, a novel method of oxynitride deposition, leveraging moderate base pressure reactive sputtering, is demonstrated for AgNW encapsulant deposition, which is compatible with roll-to-roll processes that are operated at commercial scales, and this technique can be extended to arbitrary, vacuum-compatible substrates and device architectures.

Failing Forward: Stability of Transparent Electrodes Based on Metal Nanowire Networks.

Metal nanowire (MNW)-based transparent electrode technologies have significantly matured over the last decade to become a prominent low-cost alternative to indium tin oxide (ITO). Beyond reaching the same level of performance as ITO, MNW networks offer additional advantages including flexibility and low materials cost. To facilitate adoption of MNW networks as a replacement to ITO, they must overcome their inherent stability issues while maintaining their properties and cost-effectiveness. Herein, the fundamental failure mechanisms of MNW networks are discussed in detail. Recent strategies to computationally model MNWs from the nano- to macroscale and suggest future work to capture dynamic failure to unravel mechanisms that account for convolution of the failure modes are highlighted. Strategies to characterize MNW network failure in situ and postmortem are also discussed. In addition, recent work about improving the stability of MNW networks via encapsulation is discussed. Lastly, a perspective is given on how to frame the requirements of MNW-encapsulant hybrids with reference to their target applications, namely: solar cells, transparent film heaters, sensors, and displays. A cost analysis to comment on the feasibility of implementing MNW hybrids is provided, and critical areas to focus on for future work on MNW networks are suggested.

Catalyst Self-Assembly for Scalable Patterning of Sub 10 nm Ultrahigh Aspect Ratio Nanopores in Silicon.

Nanoporous silicon (NPSi) has received significant attention for its potential to contribute to a large number of applications, but has not yet been extensively implemented because of the inability of current state-of-the-art nanofabrication techniques to achieve sufficiently small pore size, high aspect ratio, and process scalability. In this work we describe the fabrication of NPSi via a modified metal-assisted chemical etching (MACE) process in which silica-shell gold nanoparticle (SiO2-AuNP) monolayers self-assemble from solution onto a silicon substrate. Exposure to the MACE etchant solution results in the rapid consumption of the SiO2 spacer shell, leaving well-spaced arrays of bare AuNPs on the substrate surface. Particles then begin to catalyze the etching of nanopore arrays without interruption, resulting in the formation of highly anisotropic individual pores. The excellent directionality of pore formation is thought to be promoted by the homogeneous interparticle spacing of the gold core nanocatalysts, which allow for even hole injection and subsequent etching along preferred crystallographic orientations. Electron microscopy and image analysis confirm the ability of the developed technique to produce micrometer-scale arrays of sub 10 nm nanopores with narrow size distributions and aspect ratios of over 100:1. By introducing a scalable process for obtaining high aspect ratio pores in a novel size regime, this work opens the door to implementation of NPSi in numerous devices and applications.