Room Temperature Fabrication of Macroporous Lignin Membranes for the Scalable Production of Black Silicon.

Rising global demand for biodegradable materials and green sources of energy has brought attention to lignin. Herein, we report a method for manufacturing standalone lignin membranes without additives for the first time to date. We demonstrate a scalable method for macroporous (∼100 to 200 nm pores) lignin membrane production using four different organosolv lignin materials under a humid environment (>50% relative humidity) at ambient temperatures (∼20 °C). A range of different thicknesses is reported with densely porous films observed to form if the membrane thickness is below 100 nm. The fabricated membranes were readily used as a template for Ni2+ incorporation to produce a nickel oxide membrane after UV/ozone treatment. The resultant mask was etched via an inductively coupled plasma reactive ion etch process, forming a silicon membrane and as a result yielding black silicon (BSi) with a pore depth of >1 µm after 3 min with reflectance <3% in the visible light region. We anticipate that our lignin membrane methodology can be readily applied to various processes ranging from catalysis to sensing and adapted to large-scale manufacturing.

Large-Area Fabrication of Vertical Silicon Nanotube Arrays via Toroidal Micelle Self-Assembly.

We present a highly scalable, room-temperature strategy for fabricating vertical silicon nanotube arrays derived from a toroidal micelle pattern via a water vapor-induced block copolymer (BCP) self-assembly mechanism. A polystyrene-b-poly(ethylene oxide) (PS-b-PEO) BCP system can be self-assembled into toroidal micelle structures (diameter: 400-600 nm) on a PS-OH-modified substrate in a facile manner contrasting with other complex processes described in the literature. It was found that a minimum PS-b-PEO thickness of ∼86 nm is required for the toroidal self-assembly. Furthermore, a water vapor annealing treatment at room conditions (∼25 °C, 60 min) is shown to vastly enhance the ordering of micellar structures. A liquid-phase infiltration process was used to generate arrays of iron and nickel oxide nanorings. These oxide structures were used as templates for pattern transfer into the underlying silicon substrate via plasma etching, resulting in large-area 3D silicon nanotube arrays. The overall simplicity of this technique, as well as the wide potential versatility of the resulting metal structures, proves that such room-temperature synthesis routes are a viable pathway for complex nanostructure fabrication, with potential applicability in fields such as optics or catalysis.

Precise Definition of a "Monolayer Point" in Polymer Brush Films for Fabricating Highly Coherent TiO2 Thin Films by Vapor-Phase Infiltration.

In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2-4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.

MoS2 /Carbon Nanotube Core-Shell Nanocomposites for Enhanced Nonlinear Optical Performance.

Nanocomposites of layered MoS2 and multi-walled carbon nanotubes (CNTs) with core-shell structure were prepared by a simple solvothermal method. The formation of MoS2 nanosheets on the surface of coaxial CNTs has been confirmed by scanning electron microscopy, transmission electron microscopy, absorption spectrum, Raman spectroscopy, and X-ray photoelectron spectroscopy. Enhanced third-order nonlinear optical performances were observed for both femtosecond and nanosecond laser pulses over a broad wavelength range from the visible to the near infrared, compared to those of MoS2 and CNTs alone. The enhancement can be ascribed to the strong coupling effect and the photoinduced charge transfer between MoS2 and CNTs. This work affords an efficient way to fabricate novel CNTs based nanocomposites for enhanced nonlinear light-matter interaction. The versatile nonlinear properties imply a huge potential of the nanocomposites in the development of nanophotonic devices, such as mode-lockers, optical limiters, or optical switches.

Development and application of a 3D image analysis strategy for focused ion beam - Scanning electron microscopy tomography of porous soft materials.

In recent years, the potential of porous soft materials in various device technologies has increased in importance due to applications in fields, such as wearable electronics, medicine, and transient devices. However, understanding the 3-dimensional architecture of porous soft materials at the microscale remains a challenge. Herein, we present a method to structurally analyze soft materials using Focused Ion Beam - Scanning Electron Microscopy (FIB-SEM) tomography. Two materials, polymethyl methacrylate (PMMA) membrane and pine wood veneer were chosen as test-cases. FIB-SEM was successfully used to reconstruct the true topography of these materials in 3D. Structural and physical properties were subsequently deduced from the rendered 3D models. The methodology used segmentation, coupled with optimized thresholding, image processing, and reconstruction protocols. The 3D models generated pore size distribution, pore inter-connectivity, tortuosity, thickness, and curvature data. It was shown that FIB-SEM tomography provides both an informative and visual depiction of structure. To evaluate and validate the FIB-SEM reconstructions, porous properties were generated from the physical property analysis techniques, gas adsorption analysis using Brunauer-Emmett-Teller (BET) surface area analysis and mercury intrusion porosimetry (MIP) analysis. In general, the data obtained from the FIB-SEM reconstructions was well-matched with the physical data. RESEARCH HIGHLIGHTS: Porous specimens of both synthetic and biological nature, a poly(methyl methacrylate) membrane and a pine veneer respectively, are reconstructed via FIB-SEM tomography without resin-embedding. Different thresholding and reconstruction methods are explored whereby shadowing artifacts are present with the aid of free open-source software. Reconstruction data is compared to physical data: MIP, gas adsorption isotherms which are analyzed via BET and Barrett-Joyner-Halenda (BJH) analysis to yield a full picture of the materials.

Highly Ordered Porous Inorganic Structures via Block Copolymer Lithography: An Application of the Versatile and Selective Infiltration of the "Inverse" P2VP-b-PS System.

A facile and versatile strategy was developed to produce highly ordered porous metal oxide structures via block copolymer (BCP) lithography. Phase separation of poly(2-vinylpyridine)-b-polystyrene (P2VP-b-PS) was induced by solvent vapor annealing in a nonselective solvent environment to fabricate cylindrical arrays. In this work, we thoroughly analyzed the effects of the film thickness, solvent annealing time, and temperature on the ordering of a P2VP-majority system for the first time, resulting in "inverse" structures. Reflectometry, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy were used to characterize the formation of the highly ordered BCP morphology and the subsequently produced metal oxide film. At 40 min solvent annealing time, hexagonally close packed structures were produced with cylinder diameters ∼40 nm. Subsequently, the BCP films were infiltrated with different metal cations. Metal ions (Cr, Fe, Ni, and Ga) selectively infiltrated the P2VP domain, while the PS did not retain any detectable amount of metal precursor. This gave rise to a metal oxide porous structure after a UV/ozone (UVO) treatment. The results showed that the metal oxide structures demonstrated high fidelity compared to the BCP template and cylindrical domains presented a similar size to the previous PS structure. Moreover, XPS analyses revealed the complete elimination of the BCP template and confirmed the presence of the metal oxides. These metal oxides were used as hard masks for pattern transfer via dry etching as a further application. Silicon nanopores were fabricated mimicking the BCP template and demonstrated a pore depth of ∼50 nm. Ultimately, this strategy can be applied to create different inorganic nanostructures for a diverse range of applications, for example, solar cells, diodes, and integrated circuits. Furthermore, by optimizing the etching parameters, deeper structures can be obtained via ICP/RIE processes, leading to many potential applications.

Fabrication of Graphoepitaxial Gate-All-Around Si Circuitry Patterned Nanowire Arrays Using Block Copolymer Assisted Hard Mask Approach.

We demonstrate the fabrication of sub-20 nm gate-all-around silicon (Si) nanowire field effect transistor structures using self-assembly. To create nanopatterned Si feature arrays, a block-copolymer-assisted hard mask approach was utilized using a topographically patterned substrate with well-defined Si3N4 features for graphoepitaxially alignment of the self-assembled patterns. Microphase-separated long-range ordered polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block-copolymer-derived dot and line nanopatterns were achieved by a thermo-solvent approach within the substrate topographically defined channels of various widths and lengths. Solvent annealing parameters (temperature, annealing time, etc.) were varied to achieve the desired patterns. The BCP structures were modified by anhydrous ethanol to facilitate insertion of iron oxide features within the graphoepitaxial trenches that maintained the parent BCP arrangements. Vertical and horizontal ordered Si nanowire structures within trenches were fabricated using the iron oxide features as hard masks in an inductively coupled plasma (ICP) etch process. Cross-sectional micrographs depict wires of persistent width and flat sidewalls indicating the effectiveness of the mask. The aspect ratios could be varied by varying etch times. The sharp boundaries between the transistor components was also examined through the elemental mapping.

Optimization and Control of Large Block Copolymer Self-Assembly via Precision Solvent Vapor Annealing.

The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59-110 nm. This HPL phase can be controllably induced into an order-order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.