Tunable Enhanced Second-Harmonic Generation in InP-InAsP Quantum Well Nanomembranes.

Second-harmonic generation (SHG) offers a convenient approach for infrared-to-visible light conversion in tunable nanoscale light sources and optical communication. Semiconductor nanostructures offer rich possibilities to tailor their nonlinear optical properties. In this study, strong second-harmonic generation in InP nanomembranes with InAsP quantum well (QW) is demonstrated. Compared with bulk InP, up to 100 times enhancement of SHG is achieved in the short-wave infrared range. This enhancement is shown to be predominantly induced by the resonance-enhanced absorption and quantum confinement of fundamental wavelengths in the InAsP QW. The thin nanomembrane structure will also provide nanocavity enhancement for second-harmonic wavelengths. The enhanced SHG peak wavelengths can also be tuned by changing the QW composition. These findings provide an effective strategy for enhancing and manipulating the second-harmonic generation in semiconductor quantum-confined nanostructures for on-chip all-optical applications.

Gas Transport Mechanisms through Molecular Thin Carbon Nanomembranes.

Molecular thin carbon nanomembranes (CNMs) synthesized by electron irradiation induced cross-linking of aromatic self-assembled monolayers (SAMs) are promising 2D materials for the next generation of filtration technologies. Their unique properties including ultimately low thickness of ≈1 nm, sub-nanometer porosity, mechanical and chemical stability are attractive for the development of innovative filters with low energy consumption, improved selectivity, and robustness. However, the permeation mechanisms through CNMs resulting in, e.g., an ≈1000 times higher fluxes of water in comparison to helium have not been yet understood. Here, a study of the permeation of He, Ne, D2 , CO2 , Ar, O2 and D2 O using mass spectrometry in the temperature range from room temperature to ≈120 °C is studied. As a model system, CNMs made from [1″,4',1',1]-terphenyl-4-thiol SAMs are investigated. It is found out that all studied gases experience an activation energy barrier upon the permeation which scales with their kinetic diameters. Moreover, their permeation rates are dependent on the adsorption on the nanomembrane surface. These findings enable to rationalize the permeation mechanisms and establish a model, which paves the way toward the rational design not only of CNMs but also of other organic and inorganic 2D materials for energy-efficient and highly selective filtration applications.

Fast Light-Driven Motion of Polydopamine Nanomembranes.

The actuation of micro- and nanostructures controlled by external stimuli remains one of the exciting challenges in nanotechnology due to the wealth of fundamental questions and potential applications in energy harvesting, robotics, sensing, biomedicine, and tunable metamaterials. Photoactuation utilizes the conversion of light into motion through reversible chemical and physical processes and enables remote and spatiotemporal control of the actuation. Here, we report a fast light-to-motion conversion in few-nanometer thick bare polydopamine (PDA) membranes stimulated by visible light. Light-induced heating of PDA leads to desorption of water molecules and contraction of membranes in less than 140 µs. Switching off the light leads to a spontaneous expansion in less than 20 ms due to heat dissipation and water adsorption. Our findings demonstrate that pristine PDA membranes are multiresponsive materials that can be harnessed as robust building blocks for soft, micro-, and nanoscale actuators stimulated by light, temperature, and moisture level.

Advances in Functionalization of Bioresorbable Nanomembranes and Nanoparticles for Their Use in Biomedicine.

Bioresorbable nanomembranes (NMs) and nanoparticles (NPs) are powerful polymeric materials playing an important role in biomedicine, as they can effectively reduce infections and inflammatory clinical patient conditions due to their high biocompatibility, ability to physically interact with biomolecules, large surface area, and low toxicity. In this review, the most common bioabsorbable materials such as those belonging to natural polymers and proteins for the manufacture of NMs and NPs are reviewed. In addition to biocompatibility and bioresorption, current methodology on surface functionalization is also revisited and the most recent applications are highlighted. Considering the most recent use in the field of biosensors, tethered lipid bilayers, drug delivery, wound dressing, skin regeneration, targeted chemotherapy and imaging/diagnostics, functionalized NMs and NPs have become one of the main pillars of modern biomedical applications.

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena, Hybrid Materials, and Novel Functionalities.

Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO3 layer on a Si:B/Si1- x Gex :B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si1- x Gex :B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO3 at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si1- x Gex :B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO3 . The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates.

Stabilization of Sr3Al2O6 Growth Templates for Ex Situ Synthesis of Freestanding Crystalline Oxide Membranes.

A new synthetic approach has recently been developed for the fabrication of freestanding crystalline perovskite oxide nanomembranes, which involves the epitaxial growth of a water-soluble sacrificial layer. By utilizing an ultrathin capping layer of SrTiO3, here we show that this sacrificial layer, as grown by pulsed laser deposition, can be stabilized in air and therefore be used as transferrable templates for ex situ epitaxial growth using other techniques. We find that the stability of these templates depends on the thickness of the capping layer. On these templates, freestanding superconducting SrTiO3 membranes were synthesized ex situ using molecular beam epitaxy, enabled by the lower growth temperature which preserves the sacrificial layer. This study paves the way for the synthesis of an expanded selection of freestanding oxide membranes and heterostructures with a wide variety of ex situ growth techniques.

Two-Dimensional Photosensitizer Nanosheets via Low-Energy Electron Beam Induced Cross-Linking of Self-Assembled RuII Polypyridine Monolayers.

Artificial photosynthesis for hydrogen production is an important element in the search for green energy sources. The incorporation of photoactive units into mechanically stable 2D materials paves the way toward the realization of ultrathin membranes as mimics for leaves. Here we present and compare two concepts to introduce a photoactive RuII polypyridine complex into ≈1 nm thick carbon nanomembranes (CNMs) generated by low-energy electron irradiation induced cross-linking of aromatic self-assembled monolayers. The photoactive units are either directly incorporated into the CNM scaffold or covalently grafted to its surface. We characterize RuII CNMs using X-ray photoelectron, surface-enhanced Raman, photothermal deflection spectroscopy, atomic force, scanning electron microscopy, and study their photoactivity in graphene field-effect devices. Therewith, we explore the applicability of low-energy electron irradiation of metal complexes for photosensitizer nanosheet formation.

Understanding Shape Evolution and Phase Transition in InP Nanostructures Grown by Selective Area Epitaxy.

There is a strong demand for III-V nanostructures of different geometries and in the form of interconnected networks for quantum science applications. This can be achieved by selective area epitaxy (SAE) but the understanding of crystal growth in these complicated geometries is still insufficient to engineer the desired shape. Here, the shape evolution and crystal structure of InP nanostructures grown by SAE on InP substrates of different orientations are investigated and a unified understanding to explain these observations is established. A strong correlation between growth direction and crystal phase is revealed. Wurtzite (WZ) and zinc-blende (ZB) phases form along <111>A and <111>B directions, respectively, while crystal phase remains the same along other low-index directions. The polarity induced crystal structure difference is explained by thermodynamic difference between the WZ and ZB phase nuclei on different planes. Growth from the openings is essentially determined by pattern confinement and minimization of the total surface energy, regardless of substrate orientations. A novel type-II WZ/ZB nanomembrane homojunction array is obtained by tailoring growth directions through alignment of the openings along certain crystallographic orientations. The understanding in this work lays the foundation for the design and fabrication of advanced III-V semiconductor devices based on complex geometrical nanostructures.

Raman scattering study of GeSn under 〈1 0 0〉 and 〈1 1 0〉 uniaxial stress.

The application of strain into GeSn alloys can effectively modulate the band structures, thus creating novel electronic and photonic devices. Raman spectroscopy is a powerful tool for characterizing strain; however, the lack of Raman coefficient makes it difficult for accurate determination of strain in GeSn alloys. Here, we have investigated the Raman-strain function of Ge1-xSnxalong 〈1 0 0〉 and 〈1 1 0〉 directions. GeSn nanomembranes (NMs) with different Sn compositions are transfer-printed on polyethylene terephthalate substrates. External strain is introduced by bending fixtures with different radii, leading to uniaxial tensile strain up to 0.44%. Strain analysis of flexible GeSn NMs bent along 〈1 0 0〉 and 〈1 1 0〉 directions are performed by Raman spectroscopy. The linear coefficients of Raman-strain for Ge0.96Sn0.04are measured to be -1.81 and -2.60 cm-1, while those of Ge0.94Sn0.06are decreased to be -2.69 and -3.82 cm-1along 〈1 0 0〉 and 〈1 1 0〉 directions, respectively. As a result, the experimental ratio of linear coefficient (ROLC) of Ge, Ge0.96Sn0.04and Ge0.94Sn0.06are 1.34, 1.44 and 1.42, which agree well with theoretical ROLC values calculated by elastic compliances and phonon deformation potentials (PDPs). In addition, the compositional dependence of PDPs is analyzed qualitatively. These fundamental parameters are important in designing high performance strained GeSn electronic and photonic devices.

Ambipolar Resistive Switching in an Ultrathin Surface-Supported Metal-Organic Framework Vertical Heterojunction.

Memristors (MRs) are considered promising devices with the enormous potential to replace complementary metal-oxide-semiconductor (CMOS) technology, which approaches the scale limit. Efforts to fabricate MRs-based hybrid materials may result in suitable operating parameters coupled to high mechanical flexibility and low cost. Metal-organic frameworks (MOFs) arise as a favorable candidate to cover such demands. The step-by-step growth of MOFs structures on functionalized surfaces, called surface-supported metal-organic frameworks (SURMOFs), opens the possibility for designing new applications in strategic fields such as electronics, optoelectronics, and energy harvesting. However, considering the MRs architecture, the typical high porosity of these hybrid materials may lead to short-circuited devices easily. In this sense, here, it is reported for the first time the integration of SURMOF films in rolled-up scalable-functional devices. A freestanding metallic nanomembrane provides a robust and self-adjusted top mechanical contact on the SURMOF layer. The electrical characterization reveals an ambipolar resistive switching mediated by the humidity level with low-power consumption. The electronic properties are investigated with density functional theory (DFT) calculations. Furthermore, the device concept is versatile, compatible with the current parallelism demands of integration, and transcends the challenge in contacting SURMOF films for scalable-functional devices.

Controlled Electron-Induced Fabrication of Metallic Nanostructures on 1 nm Thick Membranes.

Functional hybrids comprising metallic nanostructures connected and protected by nonmetallic 2D materials are envisioned as miniaturized components for applications in optics, electronics, and magnetics. A promising strategy to build such elements is the direct writing of metallic nanostructures by focused electron beam induced processing (FEBIP) onto insulating 2D materials. Carbon nanomembranes (CNMs), produced via electron-induced crosslinking of self-assembled monolayers (SAMs), are ultrathin and flexible films; their thickness as well as their mechanical and electrical properties are determined by the specific choice of self-assembling molecules. In this work, functionalized CNMs are produced via electron beam induced deposition of Fe(CO)5 onto terphenylthiol SAMs. Clean iron nanostructures of arbitrary size and shape are deposited on the SAMs, and the SAMs are then crosslinked into CNMs. The functionalized CNMs are then transferred onto either solid substrates or onto grids to obtain freestanding metal/CNM hybrid structures. Iron nanostructures with predefined shapes on top of 1 nm thin freestanding CNMs are realized; they stay intact during the fabrication procedures and remain mechanically stable. Combining the ease and versatility of SAMs with the flexibility of FEBIP thus leads to a route for the fabrication of functional hybrid nanostructures.

Development of isoporous microslit silicon nitride membranes for sterile filtration applications.

The widely used 0.2/0.22 µm polymer sterile filters were developed for small molecule and protein sterile filtration but are not well-suited for the production of large nonprotein biological therapeutics, resulting in significant yield loss and production cost increases. Here, we report on the development of membranes with isoporous sub-0.2 µm rectangular prism pores using silicon micromachining to produce microslit silicon nitride (MSN) membranes. The very high porosity (~33%) and ultrathin (200 nm) nature of the 0.2 µm MSN membranes results in a dramatically different structure than the traditional 0.2/0.22 µm polymer sterile filter, which yielded comparable performance properties (including gas and hydraulic permeance, maximum differential pressure tolerance, nanoparticle sieving/fouling behavior). The results from bacteria retention tests, conducted according to the guidance of regulatory agencies, demonstrated that the 0.2 µm MSN membranes can be effectively used as sterile filters. It is anticipated that the results and technologies presented in this study will find future utility in the production of non-protein biological therapeutics and in other biological and biomedical applications.

Reconfigurable Vanadium Dioxide Nanomembranes and Microtubes with Controllable Phase Transition Temperatures.

Two additional structural forms, free-standing nanomembranes and microtubes, are reported and added to the vanadium dioxide (VO2) material family. Free-standing VO2 nanomembranes were fabricated by precisely thinning as-grown VO2 thin films and etching away the sacrificial layer underneath. VO2 microtubes with a range of controllable diameters were rolled-up from the VO2 nanomembranes. When a VO2 nanomembrane is rolled-up into a microtubular structure, a significant compressive strain is generated and accommodated therein, which decreases the phase transition temperature of the VO2 material. The magnitude of the compressive strain is determined by the curvature of the VO2 microtube, which can be rationally and accurately designed by controlling the tube diameter during the rolling-up fabrication process. The VO2 microtube rolling-up process presents a novel way to controllably tune the phase transition temperature of VO2 materials over a wide range toward practical applications. Furthermore, the rolling-up process is reversible. A VO2 microtube can be transformed back into a nanomembrane by introducing an external strain. Because of its tunable phase transition temperature and reversible shape transformation, the VO2 nanomembrane-microtube structure is promising for device applications. As an example application, a tubular microactuator device with low driving energy but large displacement is demonstrated at various triggering temperatures.

Low-Voltage, Flexible, and Self-Encapsulated Ultracompact Organic Thin-Film Transistors Based on Nanomembranes.

Organic thin-film transistors (OTFTs) are an ever-growing subject of research, powering recent technologies such as flexible and wearable electronics. Currently, many studies are being carried out to push forward the state-of-the-art OTFT technology to achieve characteristics that include high carrier mobility, low power consumption, flexibility, and the ability to operate under harsh conditions. Here, we tackle this task by proposing a novel OTFT architecture exploring the so-called rolled-up nanomembrane technology to fabricate low-voltage (<2 V), ultracompact OTFTs. As the OTFT gate electrode, we use strained nanomembranes, which allows all transistor components to be rolled-up and confined into a tubular-shaped tridimensional device structure with reduced footprint (ca. 90% of their planar counterpart), without any loss of electrical performance. Such an innovative architecture endows the OTFTs high mechanical flexibility (bending radius of <30 µm) and robustness-the devices can be reversibly deformed, withstanding more than 500 radial compression/decompression cycles. Additionally, the tubular device design possesses an inherent self-encapsulation characteristic that protects the OTFT active region from degradation by UV-light and hazardous vapors. The reported strategy is also shown to be compatible with different organic semiconductor materials. All of these characteristics contribute to further extending the potentialities of OTFTs, mainly toward rugged electronics.

Flexible Transient Phototransistors by Use of Wafer-Compatible Transferred Silicon Nanomembranes.

Flexible transient photodetectors, a form of optoelectronic sensors that can be physically self-destroyed in a controllable manner, could be one of the important components for future transient electronic systems. In this work, a scalable, device-first, and bottom-up thinning process enables the fabrication of a flexible transient phototransistor on a wafer-compatible transferred silicon nanomembrane. A gate modulation significantly restrains the dark current to 10-12 A. With full exposure of the light-sensitive channel, such a device yields an ultrahigh photo-to-dark current ratio of 107 with a responsivity of 1.34 A W-1 (λ = 405 nm). The use of a high-temperature degradable polymer transient interlayer realizes on-demand self-destruction of the fabricated phototransistors, which offers a solution to the technical security issue of advanced flexible electronics. Such demonstration paves a new way for designing transient optoelectronic devices with a wafer-compatible process.

Assembly and Self-Assembly of Nanomembrane Materials-From 2D to 3D.

Nanoscience and nanotechnology offer great opportunities and challenges in both fundamental research and practical applications, which require precise control of building blocks with micro/nanoscale resolution in both individual and mass-production ways. The recent and intensive nanotechnology development gives birth to a new focus on nanomembrane materials, which are defined as structures with thickness limited to about one to several hundred nanometers and with much larger (typically at least two orders of magnitude larger, or even macroscopic scale) lateral dimensions. Nanomembranes can be readily processed in an accurate manner and integrated into functional devices and systems. In this Review, a nanotechnology perspective of nanomembranes is provided, with examples of science and applications in semiconductor, metal, insulator, polymer, and composite materials. Assisted assembly of nanomembranes leads to wrinkled/buckled geometries for flexible electronics and stacked structures for applications in photonics and thermoelectrics. Inspired by kirigami/origami, self-assembled 3D structures are constructed via strain engineering. Many advanced materials have begun to be explored in the format of nanomembranes and extend to biomimetic and 2D materials for various applications. Nanomembranes, as a new type of nanomaterials, allow nanotechnology in a controllable and precise way for practical applications and promise great potential for future nanorelated products.

Ultralong-Discharge-Time Biobattery Based on Immobilized Enzymes in Bilayer Rolled-Up Enzymatic Nanomembranes.

Glucose biofuel cells (GBFCs) are highly promising power sources for implantable biomedical and consumer electronics because they provide a high energy density and safety. However, it remains a great challenge to combine their high power density with reliable long-term stability. In this study, a novel GBFC design based on the enzyme biocatalysts glucose dehydrogenase, diaphorase, and bilirubin oxidase immobilized in rolled-up titanium nanomembranes is reported. The setup delivers a maximum areal power density of ≈3.7 mW cm-2 and a stable power output of ≈0.8 mW cm-2 . The power discharges over 452 h, which is considerably longer than reported previously. These results demonstrate that the GBFC design is in principle a feasible and effective approach to solve the long-term discharge challenge for implantable biomedical device applications.

Finite element modeling to analyze TEER values across silicon nanomembranes.

Silicon nanomembranes are ultrathin, highly permeable, optically transparent and biocompatible substrates for the construction of barrier tissue models. Trans-epithelial/endothelial electrical resistance (TEER) is often used as a non-invasive, sensitive and quantitative technique to assess barrier function. The current study characterizes the electrical behavior of devices featuring silicon nanomembranes to facilitate their application in TEER studies. In conventional practice with commercial systems, raw resistance values are multiplied by the area of the membrane supporting cell growth to normalize TEER measurements. We demonstrate that under most circumstances, this multiplication does not 'normalize' TEER values as is assumed, and that the assumption is worse if applied to nanomembrane chips with a limited active area. To compare the TEER values from nanomembrane devices to those obtained from conventional polymer track-etched (TE) membranes, we develop finite element models (FEM) of the electrical behavior of the two membrane systems. Using FEM and parallel cell-culture experiments on both types of membranes, we successfully model the evolution of resistance values during the growth of endothelial monolayers. Further, by exploring the relationship between the models we develop a 'correction' function, which when applied to nanomembrane TEER, maps to experiments on conventional TE membranes. In summary, our work advances the the utility of silicon nanomembranes as substrates for barrier tissue models by developing an interpretation of TEER values compatible with conventional systems.

Thickness-Dependent Phonon Renormalization and Enhanced Raman Scattering in Ultrathin Silicon Nanomembranes.

We report on the thickness-dependent Raman spectroscopy of ultrathin silicon (Si) nanomembranes (NMs), whose thicknesses range from 2 to 18 nm, using several excitation energies. We observe that the Raman intensity depends on the thickness and the excitation energy due to the combined effects of interference and resonance from the band-structure modulation. Furthermore, confined acoustic phonon modes in the ultrathin Si NMs were observed in ultralow-frequency Raman spectra, and strong thickness dependence was observed near the quantum limit, which was explained by calculations based on a photoelastic model. Our results provide a reliable method with which to accurately determine the thickness of Si NMs with thicknesses of less than a few nanometers.

Revealing Large-Scale Homogeneity and Trace Impurity Sensitivity of GaAs Nanoscale Membranes.

III-V nanostructures have the potential to revolutionize optoelectronics and energy harvesting. For this to become a reality, critical issues such as reproducibility and sensitivity to defects should be resolved. By discussing the optical properties of molecular beam epitaxy (MBE) grown GaAs nanomembranes we highlight several features that bring them closer to large scale applications. Uncapped membranes exhibit a very high optical quality, expressed by extremely narrow neutral exciton emission, allowing the resolution of the more complex excitonic structure for the first time. Capping of the membranes with an AlGaAs shell results in a strong increase of emission intensity but also in a shift and broadening of the exciton peak. This is attributed to the existence of impurities in the shell, beyond MBE-grade quality, showing the high sensitivity of these structures to the presence of impurities. Finally, emission properties are identical at the submicron and submillimeter scale, demonstrating the potential of these structures for large scale applications.