Recording and Revealing 2.5D Nanopatterned Hidden Information on Silk Protein Bioresists.

Nanopatterning on biomaterials has attracted significant attention as it can lead to the development of biomedical devices capable of performing diagnostic and therapeutic functions while being biocompatible. Among various nanopatterning techniques, electron-beam lithography (EBL) enables precise and versatile nanopatterning in desired shapes. Various biomaterials are successfully nanopatterned as bioresists by using EBL. However, the use of high-energy electron beams (e-beams) for high-resolutive patterning has incorporated functional materials and has caused adverse effects on biomaterials. Moreover, the scattering of electrons not absorbed by the bioresist leads to proximity effects, thus deteriorating pattern quality. Herein, EBL-based nanopatterning is reported by inducing molecular degradation of amorphous silk fibroin, followed by selectively inducing secondary structures. High-resolution EBL nanopatterning is achievable, even at low-energy e-beam (5 keV) and low doses, as it minimizes the proximity effect and enables precise 2.5D nanopatterning via grayscale lithography. Additionally, integrating nanophotonic structures into fluorescent material-containing silk allows for fluorescence amplification. Furthermore, this post-exposure cross-linking way indicates that the silk bioresist can maintain nanopatterned information stored in silk molecules in the amorphous state, utilizing for the secure storage of nanopatterned information as a security patch. Based on the fabrication technique, versatile biomaterial-based nanodevices for biomedical applications can be envisioned.

Local Nanostrain Engineering of Monolayer MoS2 Using Atomic Force Microscopy-Based Thermomechanical Nanoindentation.

Strain engineering in two-dimensional materials (2DMs) has important application potential for electronic and optoelectronic devices. However, achieving precise spatial control, adjustable sizing, and permanent strain with nanoscale resolution remains challenging. Herein, a thermomechanical nanoindentation method is introduced, inspired by skin edema caused by mosquito bites, which can induce localized nanostrain and bandgap modulation in monolayer molybdenum disulfide (MoS2) transferred onto a poly(methyl methacrylate) film utilizing a heated atomic force microscopy nanotip. Via adjustment of the machining parameters, the strains of MoS2 are manipulated, achieving an average strain of ≤2.6% on the ring-shaped expansion structure. The local bandgap of MoS2 is spatially modulated using three types of nanostructures. Among them, the nanopit has the largest range of bandgap regulation, with a substantial change of 56 meV. These findings demonstrate the capability of the proposed method to create controllable and reproducible nanostrains in 2DMs.

Sub-30 nm 2D Perovskites Patterns via Block Copolymer Guided Self-Assembly for Color Conversion Optical Polarizer.

Despite the remarkable advances made in the development of 2D perovskites suitable for various high-performance devices, the development of sub-30 nm nanopatterns of 2D perovskites with anisotropic photoelectronic properties remains challenging. Herein, a simple but robust route for fabricating sub-30 nm 1D nanopatterns of 2D perovskites over a large area is presented. This method is based on nanoimprinting a thin precursor film of a 2D perovskite with a topographically pre-patterned hard poly(dimethylsiloxane) mold replicated from a block copolymer nanopattern consisting of guided self-assembled monolayered in-plane cylinders. 1D nanopatterns of various 2D perovskites (A'2 MAn -1 Pbn X3 n +1 ,A' = BA, PEA, X = Br, I) are developed; their enhanced photoluminescence (PL) quantum yields are approximately four times greater than those of the corresponding control flat films. Anisotropic photocurrent is observed because 2D perovskite nanocrystals are embedded in a topological 1D nanopattern. Furthermore, this 1D metal-coated nanopattern of a 2D perovskite is employed as a color conversion optical polarizer, in which polarized PL is developed. This is due to its capability of polarization of an incident light arising from the sub-30 nm line pattern, as well as the PL of the confined 2D perovskite nanocrystals in the pattern.

Friction Control by Deformation Mode in Nanopatterned Amorphous Carbon.

Traditionally, the manipulation of contact mechanisms has been adopted as the primary strategy to tailor the friction properties of surfaces. On the contrary, the detaching process involving the local deformation and failure at the interface has been considered relatively less important. Here, we present a new approach toward the friction control of amorphous carbon through the plasticity and resultant transition of deformation mode on nanopatterned surfaces. Depending on the topography of the nanopatterns, the mechanical responses of the surfaces alter from elastic fracture to plastic flow, through which the friction coefficient changes by a factor of 5 without manipulation of the intrinsic structure of the material.

Preparation of multilayer periodic nanopatterned WO3-based photoanode by reverse nanoimprinting for water splitting.

Photoelectrochemical (PEC) water splitting has been studied extensively as an environmentally friendly technology for hydrogen production using solar energy. WO3is considered a promising semiconducting material for photoanodes due to its high electron mobility, good hole diffusion length, and chemical stability. Periodic nanostructures of WO3have been investigated for enhancing the PEC performance of WO3-based photoanodes. In this study, facile fabrication of periodic nanostructures of WO3was achieved using reverse nanoimprint lithography, and the multilayer stacking of nanopatterned WO3film was also confirmed. The multilayer nanopatterned WO3films were used as photoanodes for PEC water splitting. The performance of the fabricated photoanode in PEC was 2 times higher than that of planar WO3film due to its higher light absorbance and lower charge transfer resistance.

Thermomechanical Nanostraining of Two-Dimensional Materials.

Local bandgap tuning in two-dimensional (2D) materials is of significant importance for electronic and optoelectronic devices but achieving controllable and reproducible strain engineering at the nanoscale remains a challenge. Here, we report on thermomechanical nanoindentation with a scanning probe to create strain nanopatterns in 2D transition metal dichalcogenides and graphene, enabling arbitrary patterns with a modulated bandgap at a spatial resolution down to 20 nm. The 2D material is in contact via van der Waals interactions with a thin polymer layer underneath that deforms due to the heat and indentation force from the heated probe. Specifically, we demonstrate that the local bandgap of molybdenum disulfide (MoS2) is spatially modulated up to 10% and is tunable up to 180 meV in magnitude at a linear rate of about -70 meV per percent of strain. The technique provides a versatile tool for investigating the localized strain engineering of 2D materials with nanometer-scale resolution.

Optimizing the Aspect Ratio of Nanopatterned Mesoporous TiO2 Thin-Film Layer to Improve Energy Conversion Efficiency of Perovskite Solar Cells.

The energy conversion efficiency (ECE) (η), current density (Jsc), open-circuit voltage (Voc), and fill factor (ff) of perovskite solar cells were studied by using the transmittance of a nanopatterned mesoporous TiO2 (mp-TiO2) thin-film layer. To improve the ECE of perovskite solar cells, a mp-TiO2 thin-film layer was prepared to be used as an electron transport layer (ETL) via the nanoimprinting method for nanopatterning, which was controlled by the aspect ratio. The nanopatterned mp-TiO2 thin-film layer had a uniform and well-designed structure, and the diameter of nanopatterning was 280 nm. The aspect ratio was controlled at the depths of 75, 97, 127, and 167 nm, and the perovskite solar cell was fabricated with different depths. The ECE of the perovskite solar cells with the nanopatterned mp-TiO2 thin-film layer was 14.50%, 15.30%, 15.83%, or 14.24%, which is higher than that of a non-nanopatterned mp-TiO2 thin-film layer (14.07%). The enhancement of ECE was attributed to the transmittance of the nanopatterned mp-TiO2 thin-film layer that is due to the improvement of the electron generation. As a result, better electron generation affected the electron density, and Jsc increased the Voc, and ff of perovskite solar cells.

Silver Nanowire-Templated Molecular Nanopatterning and Nanoparticle Assembly for Surface-Enhanced Raman Scattering.

Developing simple and cost-efficient methods for fabricating molecular patterns is of great importance in the field of nanoscience and nanotechnology. Here, a simple and convenient method was developed for fabricating nanopatterns composed of positively charged silane molecules by using silver nanowires as templates. The as-obtained silane pattern copies the shape of the silver nanowires and is only 0.7 nm thick, which can later be used for templated assembly of small molecules and nanoparticles of opposite charges. As a proof of concept, the resultant assembly could be further used for surface-enhanced Raman scattering.

The Influence of a Nanopatterned Scaffold that Mimics Abnormal Renal Mesangial Matrix on Mesangial Cell Behavior.

The alteration of mesangial matrix (MM) components in mesangium, such as type IV collagen (COL4) and type I collagen (COL1), is commonly found in progressive glomerular disease. Mesangial cells (MCs) responding to altered MM, show critical changes in cell function. This suggests that the diseased MM structure could play an important role in MC behavior. To investigate how MC behavior is influenced by the diseased MM 3D nanostructure, we fabricated the titanium dioxide (TiO2)-based nanopatterns that mimic diseased MM nanostructures. Immortalized mouse MCs were used to assess the influence of disease-mimic nanopatterns on cell functions, and were compared with a normal-mimic nanopattern. The results showed that the disease-mimic nanopattern induced disease-like behavior, including increased proliferation, excessive production of abnormal MM components (COL1 and fibronectin) and decreased normal MM components (COL4 and laminin α1). In contrast, the normal-mimic nanopattern actually resulted in cells displaying normal proliferation and the production of normal MM components. In addition, increased expressions of α-smooth muscle actin (α-SMA), transforming growth factor ß1 (TGF-ß1) and integrin α5ß1 were detected in cells grown on the disease-mimic nanopattern. These results indicated that the disease-mimic nanopattern induced disease-like cell behavior. These findings will help further establish a disease model that mimics abnormal MM nanostructures and also to elucidate the molecular mechanisms underlying glomerular disease.

Nanopatterned Scaffolds for Neural Tissue Engineering and Regenerative Medicine.

Biologically inspired approaches employing nanoengineering techniques have been influential in the progress of neural tissue repair and regeneration. Neural tissues are exposed to complex nanoscale environments such as nanofibrils. In this chapter, we summarize representative nanotechniques, such as electrospinning, lithography, and 3D bioprinting, and their use in the design and fabrication of nanopatterned scaffolds for neural tissue engineering and regenerative medicine. Nanotopographical cues in combination with other cues (e.g., chemical cues) are crucial to neural tissue repair and regeneration using cells, including various types of stem cells. Production of biologically inspired nanopatterned scaffolds may encourage the next revolution for studies aiming to advance neural tissue engineering and regenerative medicine.

High-throughput patterning of photonic structures with tunable periodicity.

A patterning method termed "RIPPLE" (reactive interface patterning promoted by lithographic electrochemistry) is applied to the fabrication of arrays of dielectric and metallic optical elements. This method uses cyclic voltammetry to impart patterns onto the working electrode of a standard three-electrode electrochemical setup. Using this technique and a template stripping process, periodic arrays of Ag circular Bragg gratings are patterned in a high-throughput fashion over large substrate areas. By varying the scan rate of the cyclically applied voltage ramps, the periodicity of the gratings can be tuned in situ over micrometer and submicrometer length scales. Characterization of the periodic arrays of periodic gratings identified point-like and annular scattering modes at different planes above the structured surface. Facile, reliable, and rapid patterning techniques like RIPPLE may enable the high-throughput and low-cost fabrication of photonic elements and metasurfaces for energy conversion and sensing applications.

Selective Functionalization of High-Resolution Cu2O Nanopatterns via Galvanic Replacement for Highly Enhanced Gas Sensing Performance.

Recently, high-resolution patterned metal oxide semiconductors (MOS) have gained considerable attention for enhanced gas sensing performance due to their polycrystalline nature, ultrasmall grain size (~5 nm), patternable properties, and high surface-to-volume ratio. Herein, we significantly enhanced the sensing performance of that patterned MOS by galvanic replacement, which allows for selective functionalization on ultrathin Cu2O nanopatterns. Based on the reduction potential energy difference between the base channel material (Cu2O) and the decorated metal ion (Pt2+), Pt could be selectively and precisely decorated onto the desired area of the Cu2O nanochannel array. Overall, the Pt-decorated Cu2O exhibited 11-fold higher NO2 (100 ppm) sensing sensitivity as compared to the non-decorated sensing channel, the while the channel device with excessive Pt doping showed complete loss of sensing properties.

Podosome Formation and Development in Monocytes Restricted by the Nanoscale Spatial Distribution of ICAM1.

We studied podosome formation and development in activated monocytes (THP1) at ICAM1 (intercellular adhesion molecule 1) nanopatterns of circular and ring-shaped domains and show that cellular binding to a preclustered ICAM1 nanopattern requires ligand patches of at least 200 nm (corresponding to 14 or more integrins). Podosome-like adhesion formation depends on the structure of the ligand pattern under the developing podosome with larger single domains promoting adhesion in a single patch and multiple smaller domains allowing podosome formation by integration of at least 2 smaller domains on either side of the podosome core. Maturation to rosette structures and recruitment of proteases were only observed with macroscopic ICAM1 presentation.

High-Resolution p-Type Metal Oxide Semiconductor Nanowire Array as an Ultrasensitive Sensor for Volatile Organic Compounds.

The development of high-performance volatile organic compound (VOC) sensor based on a p-type metal oxide semiconductor (MOS) is one of the important topics in gas sensor research because of its unique sensing characteristics, namely, rapid recovery kinetics, low temperature dependence, high humidity or thermal stability, and high potential for p-n junction applications. Despite intensive efforts made in this area, the applications of such sensors are hindered because of drawbacks related to the low sensitivity and slow response or long recovery time of p-type MOSs. In this study, the VOC sensing performance of a p-type MOS was significantly enhanced by forming a patterned p-type polycrystalline MOS with an ultrathin, high-aspect-ratio (∼25) structure (∼14 nm thickness) composed of ultrasmall grains (∼5 nm size). A high-resolution polycrystalline p-type MOS nanowire array with a grain size of ∼5 nm was fabricated by secondary sputtering via Ar(+) bombardment. Various p-type nanowire arrays of CuO, NiO, and Cr2O3 were easily fabricated by simply changing the sputtering material. The VOC sensor thus fabricated exhibited higher sensitivity (ΔR/Ra = 30 at 1 ppm hexane using NiO channels), as well as faster response or shorter recovery time (∼30 s) than that of previously reported p-type MOS sensors. This result is attributed to the high resolution and small grain size of p-type MOSs, which lead to overlap of fully charged zones; as a result, electrical properties are predominantly determined by surface states. Our new approach may be used as a route for producing high-resolution MOSs with particle sizes of ∼5 nm within a highly ordered, tall nanowire array structure.

Single-Step Soft-Imprinted Large-Area Nanopatterned Antireflection Coating.

We demonstrate an effective nanopatterned antireflection coating on glass that is based on sol-gel chemistry and large-area substrate-conformal soft-imprint technology. The printed 120 nm tall silica nanocylinders with a diameter of 245 nm in a square array with 325 nm pitch form an effective-index (n = 1.20) antireflection coating that reduces the double-sided reflection from a borosilicate glass slide from 7.35% to 0.57% (averaged over the visible spectral range) with a minimum reflectance <0.05% at 590 nm. The nanoglass coating is made using a simple process involving only spin-coating and an imprint step, without vacuum technology or annealing required. The refractive index of the nanoglass layers can be tailored over a broad range by controlling the geometry (1.002 < n < 1.44 in theory), covering a wide range that is not achievable with natural materials. We demonstrate that the nanoglass coating effectively eliminates glare from smart-phone display windows and significantly improves the efficiency of glass-encapsulated solar cells. These features, that are achieved over an angular range as wide as ±50°, together with strong hydrophobicity and mechanical durability, make nanoglass coatings a promising technology to improve the functionality of optoelectronic devices based on glass encapsulation.

Anomalous rapid defect annihilation in self-assembled nanopatterns by defect melting.

Molecular self-assembly commonly suffers from dense structural defect formation. Spontaneous defect annihilation in block copolymer (BCP) self-assembly is particularly retarded due to significant energy barrier for polymer chain diffusion and structural reorganization. Here we present localized defect melting induced by blending short neutral random copolymer chain as an unusual method to promote the defect annihilation in BCP self-assembled nanopatterns. Chemically neutral short random copolymer chains blended with BCPs are specifically localized and induce local disordered states at structural defect sites in the self-assembled nanopatterns. Such localized "defect melting" relieves the energy penalty for polymer diffusion and morphology reorganization such that spontaneous defect annihilation by mutual coupling is anomalously accelerated upon thermal annealing. Interestingly, neutral random copolymer chain blending also causes morphology-healing self-assembly behavior that can generate large-area highly ordered 10 nm scale nanopattern even upon poorly defined defective prepatterns. Underlying mechanisms of the unusual experimental findings are thoroughly investigated by three-dimensional self-consistent field theory calculation.

Differentiation of Normal and Cancer Cell Adhesion on Custom Designed Protein Nanopatterns.

Cell adhesion to the extracellular matrix is deregulated in metastasis. However, traditional surfaces used to study cell adhesion do not faithfully mimic the in vivo microenvironment. Electron beam lithography (EBL) is able to generate customized protein nanopatterns. Here, we used an EBL-based green lithography approach to fabricate homogeneous and gradient, single (fibronectin, K-casein) and double (fibronectin, laminin) active component protein nanopatterns with micrometer scale spacing to investigate differences in adhesion of breast cancer cells (BCC) and normal mammary epithelial cells (NMEC). Our results showed that as expected, in contrast to NMEC, BCC were plastic: they tolerated nonadhesion promoting regions, adapted to flow and exploited gradients better. In addition, the number of focal adhesions but not their area appeared to be the dominant parameter for regulation of cell adhesion. Our findings also demonstrated that custom designed protein nanopatterns, which can properly mimic the in vivo microenvironment, enable realistic distinction of normal and cancerous cell adhesion.

Highly Enhanced Fluorescence Signals of Quantum Dot-Polymer Composite Arrays Formed by Hybridization of Ultrathin Plasmonic Au Nanowalls.

Enhancement of the fluorescence intensity of quantum dot (QD)-polymer nanocomposite arrays is an important issue in QD studies because of the significant reduction of fluorescence signals of such arrays due to nonradiative processes in densely packed polymer chains in solid films. In this study, we enhance the fluorescence intensity of such arrays without significantly reducing their optical transparency. Enhanced fluorescence is achieved by hybridizing ultrathin plasmonic Au nanowalls onto the sidewalls of the arrays via single-step patterning and hybridization. The plasmonic Au nanowall induces metal-enhanced fluorescence, resulting in a maximum 7-fold enhancement of the fluorescence signals. We also prepare QD nanostructures of various shapes and sizes by controlling the dry etching time. In the near future, this facile approach can be used for fluorescence enhancement of colloidal QDs with plasmonic hybrid structures. Such structures can be used as optical substrates for imaging applications and for fabrication of QD-LED devices.

Nanoengineered surfaces for focal adhesion guidance trigger mesenchymal stem cell self-organization and tenogenesis.

The initial conditions for morphogenesis trigger a cascade of events that ultimately dictate structure and functions of tissues and organs. Here we report that surface nanopatterning can control the initial assembly of focal adhesions, hence guiding human mesenchymal stem cells (hMSCs) through the process of self-organization and differentiation. This process self-sustains, leading to the development of macroscopic tissues with molecular profiles and microarchitecture reminiscent of embryonic tendons. Therefore, material surfaces can be in principle engineered to set off the hMSC program toward tissuegenesis in a deterministic manner by providing adequate sets of initial environmental conditions.

Simultaneous enhancement of upconversion and downshifting luminescence via plasmonic structure.

We describe a metal nanodisk-insulator-metal (MIM) structure that enhances lanthanide-based upconversion (UC) and downshifting (DS) simultaneously. The structure was fabricated using a nanotransfer printing method that facilitates large-area applications of nanostructures for optoelectronic devices. The proposed MIM structure is a promising way to harness the entire solar spectrum by converting both ultraviolet and near-infrared to visible light concurrently through resonant-mode excitation. The overall photoluminescence enhancements of the UC and DS were 174- and 29-fold, respectively.