Ultrathin Membranes Research Articles

Regulating Entanglement Networks of Fibrillatable Binders for Sub‐20‐µm Thick, Robust, Dry‐Processed Solid Electrolyte Membranes in All‐Solid‐State Batteries

AbstractDespite significant advancements in all‐solid‐state batteries (ASSBs), the reliance on thick solid electrolyte (SE) membranes hinders their commercial viability. Although the dry process using polytetrafluoroethylene (PTFE) binder is proposed for thin SE membranes, a comprehensive understanding of the correlation between PTFE fibrillation and SE membrane quality remains lacking. Here an important guidance is provided for producing durable SE membranes that can be reduced to sub‐20‐µm thickness by regulating the entanglement networks of PTFE. While establishing fabrication parameters; shear time and shear temperature, a dominant effect of the number‐average molecular weight (Mn) on PTFE fibrillation is revealed for the first time. Moreover, the degree of PTFE fibrillation is quantified using systematic X‐ray diffraction (XRD) analysis. The SE membrane utilizing the high‐Mn PTFE binder that achieves a maximum fibrillation degree (≈98%) and thus forms highly entangled fibrous PTFE network interweaving SE particles, exhibited superior toughness. Consequently, the 18 µm thick SE membrane with 0.5 wt% high‐Mn PTFE shows a considerably higher areal conductance. The ASSB using this durable, ultrathin SE membrane outperforms its counterparts that used flimsy SE membranes or pure SE pellets. Finally, uniquely thin ASSBs demonstrate significantly improved cell‐level energy densities, showcasing the promising potential for practical ASSB fabrication.

Ultra-Thin Cation Exchange Membranes: Sulfonated Polyamide Thin-Film Composite Membranes with High Charge Density

Ultra-Thin Cation Exchange Membranes: Sulfonated Polyamide Thin-Film Composite Membranes with High Charge Density

Methanol tolerable ultrathin proton exchange membrane fabricated via in-situ ionic self-crosslinking strategy for high-performance DMFCs

Methanol tolerable ultrathin proton exchange membrane fabricated via in-situ ionic self-crosslinking strategy for high-performance DMFCs

Ultrathin cyclodextrin-based nanofiltration membrane with tunable microporosity for antibiotic desalination

Ultrathin cyclodextrin-based nanofiltration membrane with tunable microporosity for antibiotic desalination

Filling the gaps: Introducing plasticizers into π-conjugated OPE-NH2 Langmuir layers for defect-free anisotropic interfaces and membranes towards unidirectional mass, charge, or energy transfer

The construction of ultrathin membranes from linearly aligned π-electron systems is advantageous for targeted energy, charge, or mass transfer. The Langmuir-Blodgett (LB) technique enables the creation of such membranes, especially with amphiphilic π-electron systems. However, these systems often aggregate, forming rigid Langmuir monolayers with defects or holes. In this study we introduce plasticizers to effectively address this issue. To create anisotropic membranes, we used an oligo(phenylene ethynylene) derivative (OPE-NH2) as an linear amphiphile and bisphenol A di-tert-butyl ester (BPAE) as a plasticizer. We analyzed surface pressure (mean molecular area) (Π(mma)) isotherms and characterized Langmuir monolayers with Brewster Angle Microscopy (BAM), to determine the optimal miscibility of OPE-NH2 with BPAE. Detailed analysis of hole areas filled was performed through image binarization. We identified an optimal BPAE concentration of 4 mol-% in the OPE-NH2 Langmuir monolayer. Our BAM image evaluation via binarization determined the difference between the mean molecular areas of close-packed Langmuir domains and those quantified via the Π(mma) isotherm. This study presents an automated method for BAM image analysis and a new approach for fabricating defect-free anisotropic molecular monolayers of π-conjugated amphiphiles.

A Metal-Organic Framework-Based Colorimetric Sensor Array for Transcutaneous CO2 Monitoring via Lensless Imaging

Transcutaneous carbon dioxide (TcPCO2) monitoring provides a non-invasive alternative to measuring arterial carbon dioxide (PaCO2), making it valuable for various applications, such as sleep diagnostics and neonatal care. However, traditional transcutaneous monitors are bulky, expensive, and pose risks such as skin burns. To address these limitations, we have introduced a compact, cost-effective CMOS imager-based sensor for TcPCO2 detection by utilizing colorimetric reactions with metal–organic framework (MOF)-based nano-hybrid materials. The sensor, with a colorimetric sensing array fabricated on an ultrathin PDMS membrane and then adhered to the CMOS imager surface, can record real-time sensing data through image processing without the need for additional optical components, which significantly reduces the sensor’s size. Our system shows impressive sensitivity and selectivity, with a low detection limit of 26 ppm, a broad detection range of 0–2% CO2, and strong resistance to interference from common skin gases. Feasibility tests on human subjects demonstrate the potential of this MOF-CMOS imager-based colorimetric sensor for clinical applications. Additionally, its compact design and responsiveness make it suitable for sports and exercise settings, offering valuable insights into respiratory function and performance. The sensing system’s compact size, low cost, and reversible and highly sensitive TcPCO2 monitoring capability make it ideal for integration into wearable devices for remote health tracking.

Ultrathin membranes comprising polymers of intrinsic microporosity oligomers for high-performance organic solvent nanofiltration

Microporous organic polymers (MOPs) featuring chemically rigid backbones and permanent micropores are desirable for fabricating molecular selective membranes towards organics separation. However, coordinating facile film processing with high micropore persistence remains a challenge. In this paper, a low molecular weight polymers of intrinsic microporosity was rationally designed by precisely controlling the stoichiometric equilibrium of polymerization monomer. The polymers of intrinsic microporosity oligomers combine rigid and contorted structures with the aqueous solution processability, promoting the formation of 25-nm-thick polyacrylamide nanofilms with enhanced microporosity via support-free interfacial polymerization (SFIP). The resulting composite membranes have superior retention of small molecular solutes and high nonpolar and polar solvent permeances. Experiment and simulation results show that their excellent separation performance is due to substantially open and interconnected microporosity formed in the polymer networks based on rigid and contorted diamines as well as reduced film thickness. This study provides a new sight for using MOPs to construct high-microporosity membranes for precise and rapid molecular sieving.

Real-time optical thickness determination for producing ultra-thin silicon membranes using anisotropic potassium hydroxide etching

AbstractThinning silicon wafers via wet etching is a common practice in the microelectromechanical system (MEMS) industry to produce membranes and other structures Wang (Nano Lett 13(9): 4393–4398, 2013). Controlling the thickness of a membrane is a critical aspect to optimize the functionality of these devices. Our research specifically focuses on the production of bio-membranes for lung-on-a-chip (LoaC) applications. In our fabrication, it is crucial for us to determine the membranes’ thickness in a non-invasive way. This study aims to address this issue by attempting to develop a tool that uses the optical properties of light transmission through silicon to find a correlation with thickness. To find this correlation, we conducted a small experimental study where we fabricated ultra-thin membranes and captured images of the light transmission through these samples. This paper will report the correlation found between calculated average intensities of these images and measurements done using scanning electron microscopy (SEM). Graphical abstract

Rubbing-induced site-selective deposition of 2D material patterns on nanomembranes

2D-layered materials (e.g., graphene and transition metal dichalcogenides) have attracted huge attention due to their unique mechanical and electrical properties. Emerging research efforts, which seek to combine device characterization and high-resolution electron micrography analysis for 2D-layered device features, demand nano/microlithographic techniques capable of producing ordered 2D material patterns on ultrathin membranes with nanoscale thicknesses. However, such membranes are so fragile that most conventional lithographic techniques can be hardly performed on them to generate 2D material patterns. Our previous works have demonstrated that the rubbing-induced site-selective (RISS) deposition method can produce arbitrary 2D semiconductor (e.g., MoS2 and Bi2Se3) patterns on regular device substrates. This fabrication route prevents the vulnerable 2D-layered structures from the detrimental damage introduced by plasma etching and resist-based lithography processes. In this work, we explore the applicability of RISS for directly producing 2D material patterns on nanomembranes. Specifically, this work shows that a polymeric interfacing layer on the rubbing template features, which can effectively prevent stress concentration during the rubbing process, is crucial to successful implementation of RISS processes on nanomembranes. Furthermore, we carried out the mechanics simulation of the Von Mises stress and pressure distribution on the RISS-processed membrane to identify the optimal rubbing load, which can generate sufficient triboelectric charge for material deposition but no damage to the membrane. Using this approach, we have successfully demonstrated the deposition of Bi2Se3 patterns on 25 nm SiOx nanomembranes and high-resolution transmission electron micrography characterization of the crystallographic structures.

Precision-induced localized molten liquid metal stamps for damage-free transfer printing of ultrathin membranes and 3D objects

Transfer printing, a crucial technique for heterogeneous integration, has gained attention for enabling unconventional layouts and high-performance electronic systems. Elastomer stamps are typically used for transfer printing, where localized heating for elastomer stamp can effectively control the transfer process. A key challenge is the potential damage to ultrathin membranes from the contact force of elastic stamps, especially with fragile inorganic nanomembranes. Herein, we present a precision-induced localized molten technique that employs either laser-induced transient heating or hotplate-induced directional heating to precisely melt solid gallium (Ga). By leveraging the fluidity of localized molten Ga, which provides gentle contact force and exceptional conformal adaptability, this technique avoids damage to fragile thin films and improves operational reliability compared to fully liquefied Ga stamps. Furthermore, the phase transition of Ga provides a reversible adhesion with high adhesion switchability. Once solidified, the Ga stamp hardens and securely adheres to the micro/nano-membrane during the pick-up process. The solidified stamp also exhibits the capability to maneuver arbitrarily shaped objects by generating a substantial grip force through the interlocking effects. Such a robust, damage-free, simply operable protocol illustrates its promising capabilities in transfer printing diverse ultrathin membranes and objects on complex surfaces for developing high-performance unconventional electronics.

Ultrathin Self-Healing Nanofibrous Membrane with a Hierarchical Confined Structure for Biomimetic Epidermal Electrodes.

Integrating self-healing capabilities into epidermal electrodes is crucial to improving their reliability and longevity. Self-healing nanofibrous materials are considered an ideal candidate for constructing ultrathin, long-lasting wearable epidermal electrodes due to their lightweight and high breathability. However, due to the strong interaction between fibers, self-healing nanofiber membranes cannot exist stably. Therefore, the development of self-healing and breathable nanofibrous epidermal electrodes still remains a major challenge. Here, a hierarchical confinement strategy that combines molecular and spatial confinement to overcome supramolecular hydrogen bonding between self-healing nanofibers is reported, and an ultrathin self-healing nanofibrous epidermal electrode with a neural net-like structure is developed. It can achieve real-time monitoring of electrophysiological signals through long-term conformal attachment to skin or plants and has no adverse effects on skin health or plant growth. Given the almost imperceptible nature of epidermal electrodes to users and plants, it lays the foundation for the development of biocompatible, self-healing, wearable, flexible electronics.

Direct-bonded diamond membranes for heterogeneous quantum and electronic technologies

Diamond has superlative material properties for a broad range of quantum and electronic technologies. However, heteroepitaxial growth of single crystal diamond remains limited, impeding integration and evolution of diamond-based technologies. Here, we directly bond single-crystal diamond membranes to a wide variety of materials including silicon, fused silica, sapphire, thermal oxide, and lithium niobate. Our bonding process combines customized membrane synthesis, transfer, and dry surface functionalization, allowing for minimal contamination while providing pathways for near unity yield and scalability. We generate bonded crystalline membranes with thickness as low as 10 nm, sub-nm interfacial regions, and nanometer-scale thickness variability over 200 by 200 μm2 areas. We measure spin coherence times T2 for nitrogen vacancy centers in 150 nm-thick bonded membranes of up to 623 ± 21 μs, suitable for advanced quantum applications. We demonstrate multiple methods for integrating high quality factor nanophotonic cavities with the diamond heterostructures, highlighting the platform versatility in quantum photonic applications. Furthermore, we show that our ultra-thin diamond membranes are compatible with total internal reflection fluorescence (TIRF) microscopy, which enables interfacing coherent diamond quantum sensors with living cells while rejecting unwanted background luminescence. The processes demonstrated herein provide a full toolkit to synthesize heterogeneous diamond-based hybrid systems for quantum and electronic technologies.

Nacre-inspired graphene oxide/polyethyleneimine-based ultra-thin heterogeneous superwetting membrane for highly stable separation of oil-in-water emulsions

Since the massive discharge of oily wastewater seriously affects both humans and natural development, the performance of conventional membrane materials in terms of interfacial stability and antifouling in the treatment of surfactant-containing emulsified oily wastewater is a major challenge. In this work, a novel nacre-inspired graphene oxide/polyethyleneimine-based ultra-thin chemically heterogeneous superwetting membrane was fabricated through vacuum-assisted self-assembly and post-modification methods for oil-in-water emulsion separation. The nacre-inspired heterogeneous membrane exhibited superhydrophilicity, underwater superoleophobicity (underwater oil contact angle was 157.7°), excellent crude oil adhesion resistance, high acid/alkaline stability, outstanding salt resistance, and good mechanical properties (Young’s modulus 1391.7 MPa). The heterogeneous membranes showed separation efficiencies of more than 99.9 % for a range of oil-in-water emulsions. The high-value membranes could achieve the permeances of 917–1256 L m−2h−1 bar−1 for pure water and 339.7–577 L m−2h−1 bar−1 for emulsion through a dead-end filter device, with the optimal long-term stable permeance only decreasing by 30.0 % compared to the initial value. After six test cycles, the membrane’s antifouling and self-cleaning properties were enhanced by constructing heterogeneous superwetting properties, and the flux recovery rate remained at 96.5 %. All of these results indicated that this method provides new ideas for the design and fabrication of highly stable and antifouling membrane materials.

Rapid Assessment of Biomarkers on Single Extracellular Vesicles Using "Catch and Display" on Ultrathin Nanoporous Silicon Nitride Membranes.

Extracellular vesicles (EVs) are particles released from cells that facilitate intercellular communication and have tremendous diagnostic and therapeutic potential. Bulk assays lack the sensitivity to detect rare EV subsets relevant to disease, and while single EV analysis techniques remedy this, they are often undermined by complicated detection schemes and prohibitive instrumentation. To address these issues, a microfluidic technique for EV characterization called "catch and display for liquid biopsy (CAD-LB)" is proposed. In this method, minimally processed samples are pipette-injected and fluorescently labeled EVs are captured in the nanopores of an ultrathin membrane. This enables the rapid assessment of EV number and biomarker colocalization by light microscopy. Here, nanoparticles are used to define the accuracy and dynamic range for counting and colocalization. The same assessments are then made for purified EVs and for unpurified EVs in plasma. Biomarker detection is validated using CD9 and Western blot analysis to confirm that CAD-LB accurately reports relative protein expression levels. Using unprocessed conditioned media,CAD-LB captures the known increase in EV-associated ICAM-1 following endothelial cell cytokine stimulation. Finally, to demonstrate CAD-LB's clinical potential, EV biomarkers indicative of immunotherapy responsiveness are successfully detected in the plasma of bladder cancer patients treated with immune checkpoint blockade.

The Influence of Membrane Thickness and Catalyst Loading on Performance of Proton Exchange Membrane Fuel Cells

This paper explores the influence of membrane thickness and catalyst loading on fuel cell performance of commercially relevant membrane electrode assemblies (MEAs). A systematic study was carried out with MEAs comprised of commercially available Pt/C electrocatalysts and reinforced PFSA membranes to better understand the practical limitations of incorporating low platinum loadings and ultra-thin membranes in commercially viable MEA designs. Three different MEA configurations were compared where membrane thickness was either 15 or 10 μm and cathode catalyst loading was either 0.4 or 0.1 mgPt cm−2. Extensive in situ electrochemical characterization was carried out to extract the relevant physical and electrochemical parameters of each MEA configuration. By changing only one variable at a time, i.e., either thickness or catalyst loading, it was possible to deconvolute the specific contributions of membrane thickness and catalyst loading on fuel cell performance. Interestingly, as membrane thickness was reduced below 15 μm, no significant changes in fuel cell performance were observed as membrane interfacial effects begin to dominate compared to bulk transport effects. Conversely, reducing catalyst layer loading from 0.4 to 0.1 mgPt cm−2 introduces significant polarization losses attributed to a combination of kinetic and mass transport effects.

Highly Anion-Conductive Viologen-Based Two-Dimensional Polymer Membranes as Nanopower Generators.

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6-20 nm), as well as low charge density (<4.5 mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55 W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Concentrated solar thermoelectric power generator equipped with a novel ultrathin wet porous membrane cooling technique; experimental study

One side of any thermoelectric power generator (TEG) is hot while the other side should always stay cold. The higher the temperature difference, the greater the power generation. This paper offers a particular ultrathin wet porous membrane (UWPM) as a new cooling method for a solar thermoelectric power generator. According to the graphical abstract, the membrane has a capillary-wicking feature on one side, making it possible to be soaked spontaneously and create a steady thin water film on the ceramic layer of the thermoelectric, thereby serving as an energy-free, enthalpy of vaporization-based cooling method (surface vaporization). Interestingly, water is replenished spontaneously as long as the water exists in the tank. The suggested mechanism is tested under two weather conditions: one hot, dry day (ambient air around 40 °C) and one moderate day (ambient air around 30 °C), with different air speeds between 1.5 and 4.5 m/s to simulate different wind speeds in real applications. Power, cold side surface temperature, maximum conversion efficiency, etc., are measured, evaluated, discussed, and compared with the common fin-pin heatsink/fan thermal management tool. Notably, the implementation of the UWPM demonstrates a substantial enhancement in thermoelectric generator performance. It is noted that the lowest temperature that can be obtained through vaporization can be colder than ambient air temperature, approaching the wet-bulb temperature. The UWPM keeps the cold side temperature up to 10 degrees colder than that achieved in the heatsink method. This is why the generated power by the TEG is around 2.5 times higher when utilizing the UWPM. Furthermore, unlike the fin-pin heatsink (FPH) thermal management tool, warmer weather conditions do not diminish the cooling quality of the UWPM method. Indeed, the cold side temperature on a hot, dry day is almost the same as that on a moderate day using the UWPM technique. This is because hot ambient temperature induces greater and easier vaporization, leading to a higher cooling effect.

Modulating low-temperature interfacial polymerization with NaHCO3 for high-performance ultrathin nanofiltration membranes

Conventional interfacial polymerization (IP) encounters significant challenges in achieving the desired nanofiltration (NF) membrane structure, owing to uncontrolled diffusion and ultrafast polymerization. Our study introduced carbonates into the low-temperature interfacial polymerization (LTIP) process to precisely regulate the diffusion of amine monomers and polymerization kinetics. Carbonates in the aqueous phase restrict the diffusion of amine monomers while promoting the generation of nanobubbles. Further utilization of the low-temperature oil phase not only retards polymerization but also facilitates the formation of foam nanostructures in the polyamide layer. Density functional theory calculations and molecular dynamics simulations revealed the mechanisms underlying the regulation of amine monomer diffusion and gas-bubble release by carbonates and LTIP. The fabricated membrane has a smoother, ultrathin separation layer while maintaining a high permeability of 35.0 L·m−2·h−1·bar−1 (nearly doubled compared with the pristine membrane) and high Na2SO4 rejection of 99.5 %. This study confirms the practicality of the carbonate-modulated LTIP strategy.

In situ generation of (sub) nanometer pores in MoS2 membranes for ion-selective transport

Ion selective membranes are fundamental components of biological, energy, and computing systems. The fabrication of solid-state ultrathin membranes that can separate ions of similar size and the same charge with both high selectivity and permeance remains a challenge, however. Here, we present a method, utilizing the application of a remote electric field, to fabricate a high-density of (sub)nm pores in situ. This method takes advantage of the grain boundaries in few-layer polycrystalline MoS2 to enable the synthesis of nanoporous membranes with average pore size tunable from <1 to ~4 nm in diameter (with in situ pore expansion resolution of ~0.2 nm2 s−1). These membranes demonstrate selective transport of monovalent ions (K+, Na+ and Li+) as well as divalent ions (Mg2+ and Ca2+), outperforming existing two-dimensional material nanoporous membranes that display similar total permeance. We investigate the mechanism of selectivity using molecular dynamics simulations and unveil that the interactions between cations and the sluggish water confined to the pore, as well as cation-anion interactions, result in the different transport behaviors observed between ions.

Binary-Cooperative Ultrathin Porous Membrane for Gas Separation.

The construction of ultrathin porous membranes with stable structures is critical for achieving efficient gas separation. Inspired by the binary-cooperative structural features of bones and teeth-composed of rigid hydroxyapatite and flexible collagen, which confer excellent mechanical strength-a binary-cooperative porous membrane constructed with gel-state zeolitic imidazolate frameworks (g-ZIFs), synthesized using a metal-gel-induced strategy, is proposed. The enlarged cavity size and flexible frameworks of the g-ZIF nanoparticles significantly improve gas adsorption and diffusion, respectively. After thermal treatment, the coordination structures forming rigid segments in the g-ZIF membranes appear at the stacked g-ZIF boundaries, exhibiting a higher Young's modulus than the g-ZIF nanoparticles, denoted as the flexible segments. The g-ZIF membranes demonstrate excellent tensile and compression resistances, attributed to the effective translation of binary-cooperative effects of rigidity and flexibility into the membranes. The resulting dual-aperture structure, composed of g-ZIF nanoparticles surrounded by nanoscale apertures at the boundaries, yields a membrane with a stable CO2 permeance of 4834 GPU and CO2/CH4 selectivity of 90 within 3.0MPa.