Bulk-suppressed and surface-sensitive Raman scattering by transferable plasmonic membranes with irregular slot-shaped nanopores.

Raman spectroscopy enables the non-destructive characterization of chemical composition, crystallinity, defects, or strain in countless materials. However, the Raman response of surfaces or thin films is often weak and obscured by dominant bulk signals. Here we overcome this limitation by placing a transferable porous gold membrane, (PAuM) on the surface of interest. Slot-shaped nanopores in the membrane act as plasmonic antennas and enhance the Raman response of the surface or thin film underneath. Simultaneously, the PAuM suppresses the penetration of the excitation laser into the bulk, efficiently blocking its Raman signal. Using graphene as a model surface, we show that this method increases the surface-to-bulk Raman signal ratio by three orders of magnitude. We find that 90% of the Raman enhancement occurs within the top 2.5 nm of the material, demonstrating truly surface-sensitive Raman scattering. To validate our approach, we quantify the strain in a 12.5 nm thin Silicon film and analyze the surface of a LaNiO3 thin film. We observe a Raman mode splitting for the LaNiO3 surface-layer, which is spectroscopic evidence that the surface structure differs from the bulk. These results validate that PAuM gives direct access to Raman signatures of thin films and surfaces.

Freestanding and Permeable Nanoporous Gold Membranes for Surface-Enhanced Raman Scattering.

Surface-enhanced Raman spectroscopy (SERS) demands reliable, high-enhancement substrates in order to be used in different fields of application. Here we introduce freestanding porous gold membranes (PAuM) as easy-to-produce, scalable, mechanically stable, and effective SERS substrates. We fabricate large-scale sub-30 nm thick PAuM that form freestanding membranes with varying morphologies depending on the nominal gold thickness. These PAuM are mechanically stable for pressures up to more than 3 bar and exhibit surface-enhanced Raman scattering with local enhancement factors from 104 to 105, which we demonstrate by wavelength-dependent and spatially resolved Raman measurements using graphene as a local Raman probe. Numerical simulations reveal that the enhancement arises from individual, nanoscale pores in the membrane acting as optical slot antennas. Our PAuM are mechanically stable, provide robust SERS enhancement for excitation power densities up to 106 W cm-2, and may find use as a building block in SERS-based sensing applications.

Ab Initio Energetic Barriers of Gas Permeation across Nanoporous Graphene.

Realizing membranes of atomic thickness functioning reliably constitutes a giant leap forward for a plethora of applications where the efficient separation of fluid constituents at the molecular level is critical. Here, by employing density functional theory, we explore the energy landscape of typical gas molecules attempting permeation through graphene nanopores and determine the minimum energy permeation pathways, based on the precise knowledge of the related molecular level interactions. With this approach we investigate two basic permeation routes: direct permeation and surface-based transport. We find that for subnanometer pores, the diffusion barrier of direct and surface transport depends on the pore chemical functionalization, while the molecule pore permeation barrier is independent of the gas-pore approach due to the overlap of surface and direct diffusion paths over the pore center. The overall minimum energy permeation pathway of He, H2, CO2, and CH4 molecules, across nanopores of different dimensions and chemical functionalization, defines the pore diameter (∼1.2 nm) below which effusion theory is inaccurate, as well as the critical pore diameter (∼0.8 nm) required to achieve positive permeation barriers driving molecular sieving. We determine that achieving positive permeation barriers required for high selectivity gas separation is inseparably combined with postpermeation desorption barriers due to attractive van der Waals interactions. The discovered permeation energetics are pore-molecule-specific and are incorporated into an analytical model extending existing theory. Our results provide a scientific background for rational pore design in graphene membranes, which can lead to gas separation at a commercially relevant performance level.

Selective Etching of Graphene Membrane Nanopores: From Molecular Sieving to Extreme Permeance.

Two-dimensional materials are the essential building blocks of breakthrough membrane technologies due to minimal permeation barriers across atomically thin pores. Tunable pore size fabrication combined with independently controlled pore number density is necessary for outstanding performance but remains a challenge. There is a great need for parallel, upscalable methods that can control pore size from sub-nm to >5 nm, a pore size range required for membranes with effective molecular separation. Here we report a dry, facile, and scalable process introducing atomic defects by design, followed by selective etching of graphene edge atoms able to controllably expand the nanopore dimensions from sub-nm to 5 nm. The attainable average pore sizes at 1015 m-2 pore density promise applicability to various separation applications. We investigate the gas permeation and separation mechanisms, finding that these membranes display molecular sieving (H2/CH4 separation factor = 9.3; H2 permeance = 3370 gas permeation units (GPU)) and reveal the presence of interweaved transport phenomena of pore chemistry, surface flow, and gas molecule momentum transfer. We observe the smooth transition from molecular sieving to effusion at unprecedented permeance (H2/CH4 separation factor = 3.7; H2 permeance = 107 GPU). Our scalable graphene membrane fabrication approach in combination with sub-5 nm pores opens a new route employing 2D membranes to study gas transport and effectively paving the way to industrial applications.

Assessing the Thickness-Permeation Paradigm in Nanoporous Membranes.

Driven by the need of maximizing performance, membrane nanofabrication strives for ever thinner materials aiming to increase permeation while evoking inherent challenges stemming from mechanical stability and defects. We investigate this thickness rationale by studying viscous transport mechanisms across nanopores when transitioning the membrane thickness from infinitely thin to finite values. We synthesize double-layer graphene membranes containing pores with diameters from ∼6 to 1000 nm to investigate liquid permeation over a wide range of viscosities and pressures. Nanoporous membranes with thicknesses up to 90 nm realized by atomic layer deposition demonstrate dominance of the entrance resistance for aspect ratios up to one. Liquid permeation across these atomically thin pores is limited by viscous dissipation at the pore entrance. Independent of thickness and universal for porous materials, this entrance resistance sets an upper bound to the viscous transport. Our results imply that membranes with near-ultimate permeation should feature rationally selected thicknesses based on the target solute size for applications ranging from osmosis to microfiltration and introduce a proper perspective to the pursuit of ever thinner membranes.

Multifunctional wafer-scale graphene membranes for fast ultrafiltration and high permeation gas separation.

Reliable and large-scale manufacturing routes for perforated graphene membranes in separation and filtration remain challenging. We introduce two manufacturing pathways for the fabrication of highly porous, perforated graphene membranes with sub-100-nm pores, suitable for ultrafiltration and as a two-dimensional (2D) scaffold for synthesizing ultrathin, gas-selective polymers. The two complementary processes-bottom up and top down-enable perforated graphene membranes with desired layer number and allow ultrafiltration applications with liquid permeances up to 5.55 × 10-8 m3 s-1 Pa-1 m-2. Moreover, thin-film polymers fabricated via vapor-liquid interfacial polymerization on these perforated graphene membranes constitute gas-selective polyimide graphene membranes as thin as 20 nm with superior permeances. The methods of controlled, simple, and reliable graphene perforation on wafer scale along with vapor-liquid polymerization allow the expansion of current 2D membrane technology to high-performance ultrafiltration and 2D material reinforced, gas-selective thin-film polymers.