Nanopatterning Approach Research Articles

Orthogonally Spin-Coated Bilayer Films for Photochemical Immobilization and Patterning of Sub-10-Nanometer Polymer Monolayers

Versatile and spatiotemporally controlled methods for decorating surfaces with monolayers of attached polymers are broadly impactful to many technological applications. However, current materials are usually designed for very specific polymer/surface chemistries and, as a consequence, are not very broadly applicable and/or do not rapidly respond to high-resolution stimuli such as light. We describe here the use of a polymeric adhesion layer, poly(styrene sulfonyl azide-alt-maleic anhydride) (PSSMA), which is capable of immobilizing a 1-7 nm thick monolayer of preformed, inert polymers via photochemical grafting reactions. Solubility of PSSMA in very polar solvents enables processing alongside hydrophobic polymers or solutions and by extension orthogonal spin-coating deposition strategies. Therefore, these materials and processes are fully compatible with photolithographic tools and can take advantage of the immense manufacturing scalability they afford. For example, the thicknesses of covalently grafted poly(styrene) obtained after seconds of exposure are quantitatively equivalent to those obtained by physical adsorption after hours of thermal equilibration. Sequential polymer grafting steps using photomasks were used to pattern different regions of surface energy on the same substrate. These patterns spatially controlled the self-assembled domain orientation of a block copolymer possessing 21 nm half-periodicity, demonstrating hierarchical synergy with leading-edge nanopatterning approaches.

High-Energy Surface and Volume Plasmons in Nanopatterned Sub-10 nm Aluminum Nanostructures.

In this work, we use electron energy-loss spectroscopy to map the complete plasmonic spectrum of aluminum nanodisks with diameters ranging from 3 to 120 nm fabricated by high-resolution electron-beam lithography. Our nanopatterning approach allows us to produce localized surface plasmon resonances across a wide spectral range spanning 2-8 eV. Electromagnetic simulations using the finite element method support the existence of dipolar, quadrupolar, and hexapolar surface plasmon modes as well as centrosymmetric breathing modes depending on the location of the electron-beam excitation. In addition, we have developed an approach using nanolithography that is capable of meV control over the energy and attosecond control over the lifetime of volume plasmons in these nanodisks. The precise measurement of volume plasmon lifetime may also provide an opportunity to probe and control the DC electrical conductivity of highly confined metallic nanostructures. Lastly, we show the strong influence of the nanodisk boundary in determining both the energy and lifetime of surface plasmons and volume plasmons locally across individual aluminum nanodisks, and we have compared these observations to similar effects produced by scaling the nanodisk diameter.

Polymer flow and filling behavior for electroosmosis-driven nanoimprint lithography

Electroosmosis-driven nanoimprint lithography (NIL) is an emerging nanopatterning approach which has shown great potential and unique strength in large-area nanoimprinting, fabricating high-aspect-ratio micro/nanostructures, patterning fragile substrates and non-flat surface. However, compared to the conventional pressure-driven NIL and the electrocapillary force-driven UV-imprinting, there is a big difference for such novel electroosmotic flow driven imprinting process. This paper investigated the mechanism, influencing factors and laws of polymer flow and filling behavior for the electroosmosis-driven nanoimprinting. Based on the principle of electroosmosis-driven micro flows, a theoretical model estimated body force was established. And the model of filling velocity and the model of filling time were derived. Furthermore, the dynamic filling process of electroosmosis-driven NIL, influence and laws of polymer flow and filling behavior regarding the imprint process parameters, the feature patterns and the properties of polymer were revealed by numerical simulation using COMSOL Multiphysics simulation software. These findings are valuable in providing a theoretical basis for electroosmosis-driven nanoimprinting, optimizing imprinting process and further enhancing the performance of the new patterning method.

Isolation and Mechanical Measurements of Myofibrils from Human Induced Pluripotent Stem Cell-Derived Cardiomyocytes.

SummaryTension production and contractile properties are poorly characterized aspects of excitation-contraction coupling of human induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CMs). Previous approaches have been limited due to the small size and structural immaturity of early-stage hiPSC-CMs. We developed a substrate nanopatterning approach to produce hiPSC-CMs in culture with adult-like dimensions, T-tubule-like structures, and aligned myofibrils. We then isolated myofibrils from hiPSC-CMs and measured the tension and kinetics of activation and relaxation using a custom-built apparatus with fast solution switching. The contractile properties and ultrastructure of myofibrils more closely resembled human fetal myofibrils of similar gestational age than adult preparations. We also demonstrated the ability to study the development of contractile dysfunction of myofibrils from a patient-derived hiPSC-CM cell line carrying the familial cardiomyopathy MYH7 mutation (E848G). These methods can bring new insights to understanding cardiomyocyte maturation and developmental mechanical dysfunction of hiPSC-CMs with cardiomyopathic mutations.

Alkali-templated surface nanopatterning of chalcogenide thin films: a novel approach toward solar cells with enhanced efficiency.

Concepts of localized contacts and junctions through surface passivation layers are already advantageously applied in Si wafer-based photovoltaic technologies. For Cu(In,Ga)Se2 thin film solar cells, such concepts are generally not applied, especially at the heterojunction, because of the lack of a simple method yielding features with the required size and distribution. Here, we show a novel, innovative surface nanopatterning approach to form homogeneously distributed nanostructures (<30 nm) on the faceted, rough surface of polycrystalline chalcogenide thin films. The method, based on selective dissolution of self-assembled and well-defined alkali condensates in water, opens up new research opportunities toward development of thin film solar cells with enhanced efficiency.

Patterning of magnetic thin films and multilayers using nanostructured tantalum gettering templates.

This work demonstrates that a nonmagnetic thin film of cobalt oxide (CoO) sandwiched between Ta seed and capping layers can be effectively reduced to a magnetic cobalt thin film by annealing at 200 °C, whereas CoO does not exhibit ferromagnetic properties at room temperature and is stable at up to ∼400 °C. The CoO reduction is attributed to the thermodynamically driven gettering of oxygen by tantalum, similar to the exothermic reduction-oxidation reaction observed in thermite systems. Similarly, annealing at 200 °C of a nonmagnetic [CoO/Pd]N multilayer thin film sandwiched between Ta seed and Ta capping layers results in the conversion into a magnetic [Co/Pd]N multilayer, a material with perpendicular magnetic anisotropy that is of interest for magnetic data storage applications. A nanopatterning approach is introduced where [CoO/Pd]N multilayers is locally reduced into [Co/Pd]N multilayers to achieve perpendicular magnetic anisotropy nanostructured array. This technique can potentially be adapted to nanoscale patterning of other systems for which thermodynamically favorable combination of oxide and gettering layers can be identified.

High-Resolution Metal Nanopatterning by Means of Switchable Block Copolymer Templates.

In this review, recent developments in the fabrication of hexagonal and parallel ordered arrays of metallic nanodomains on a substrate are described. We focus on the nanopatterning approach by means of switchable block copolymer thin films. This approach is highly advantageous, because it can lead to extremely regular patterns with metal subunits of only a few nanometers in diameter and center-to-center distances of tens of nanometers. Hence, the resulting 1D or 2D periodic arrays of metal nanodots and nanowires on silicon substrates can be fabricated with extremely high unit densities and on very large areas. The templated deposition of presynthesized metal nanoparticles on functional block copolymers is described in detail. Current challenges are discussed and an outlook for further developments is given.

Theory and simulations of peel demolding for large-area nanoimprint lithography

Nanoimprint lithography (NIL) is an emerging nanopatterning approach for producing large-area micro/nano scale structures with low cost, high throughput and high resolution. Demolding has now been considered as one of the most challenging issues for large area NIL, and a bottleneck hindering the industrialization of full wafer NIL. Peel demolding mode has been proven to be an effective way implementing large area nanoimprinting. This paper investigated the theoretical model and numerical simulation of peel demolding for large are NIL. A general model estimating demolding force was established based on the combination of the strain energy method and the conservation of energy in demolding stage. The required separating force for vertical demolding of grating patterns was achieved using the proposed model. Furthermore, the influence of the properties of mold materials and the aspect ratio of feature patterns for peel demolding was revealed by numerical simulation using ABAQUS software. These findings are valuable in providing a theoretical basis for large area NIL, optimizing demolding process and further enhancing the performance of full wafer NIL tool.

Nanomotor lithography.

The rapid miniaturization of devices and machines has fuelled the evolution of advanced fabrication techniques. However, the complexity and high cost of the state-of-the-art high-resolution lithographic systems are prompting unconventional routes for nanoscale patterning. Inspired by natural nanomachines, synthetic nanomotors have recently demonstrated remarkable performance and functionality. Here we report a new nano-patterning approach, named 'nanomotor lithography', which translates the autonomous movement trajectories of nanomotors into controlled surface features. As a proof of principle, we use metallic nanowire motors as mobile nanomasks and Janus sphere motors as near-field nanolenses to manipulate light beams for generating a myriad of nanoscale features through modular nanomotor design. The complex spatially defined nanofeatures using these dynamic nanoscale optical elements can be achieved through organized assembly and remote guidance of multiple nanomotors. Such ability to transform predetermined paths of moving nanomachines to defined surface patterns provides a unique nanofabrication platform for creating diverse nanodevices.

Nanoporous alumina as templates for multifunctional applications

Due to its manufacturing and size tailoring ease, porous anodic alumina (PAA) templates are an elegant physical-chemical nanopatterning approach and an emergent alternative to more sophisticated and expensive methods currently used in nanofabrication. In this review, we will describe the ground work on the fabrication methods of PAA membranes and PAA-based nanostructures. We will present the specificities of the electrochemical growth processes of multifunctional nanomaterials with diversified shapes (e.g., nanowires and nanotubes), and the fabrication techniques used to grow ordered nanohole arrays. We will then focus on the fabrication, properties and applications of magnetic nanostructures grown on PAA and illustrate their dependence on internal (diameter, interpore distance, length, composition) and external (temperature and applied magnetic field intensity and direction) parameters. Finally, the most outstanding experimental findings on PAA-grown nanostructures and their trends for technological applications (sensors, energy harvesting, metamaterials, and biotechnology) will be addressed.

Polymer-free patterning of graphene at sub-10-nm scale by low-energy repetitive electron beam.

A polymer-free technique for generating nanopatterns on both synthesized and exfoliated graphene sheets is proposed and demonstrated. A low-energy (5-30 keV) scanning electron beam with variable repetition rates is used to etch suspended and unsuspended graphene sheets on designed locations. The patterning mechanisms involve a defect-induced knockout process in the initial etching stage and a heat-induced curling process in a later stage. Rough pattern edges appear due to inevitable stochastic knockout of carbon atoms or graphene structure imperfection and can be smoothed by thermal annealing. By using this technique, the minimum feature sizes achieved are about 5 nm for suspended and 7 nm for unsuspended graphene. This study demonstrates a polymer-free direct nanopatterning approach for graphene.

Sub-100-nm Nanoparticle Arrays with Perfect Ordering and Tunable and Uniform Dimensions Fabricated by Combining Nanoimprinting with Ultrathin Alumina Membrane Technique

This work reports a nonlithographic nanopatterning approach to fabricate perfectly ordered nanoparticle arrays with tunable and uniform dimensions from about 30 to 80 nm and strict periods of 100 nm in a square lattice on large-area substrates by combining nanoimprinting with ultrathin alumina membrane technique. There is no requirement of any organic layer to support an ultrathin membrane in our novel route, which totally addressed the problems of nonuniform pores in prepatterned alumina templates and contamination during sample preparation, and thus is indispensable for our fabrication of ideally regular nanoparticle arrays on various kinds of substrates (such as flexible plastic). The effect of imprinted pressure on the prepatterning of Al foil was also studied in order to ensure the reusability of the precious imprinting stamps. This simple but efficient method provides a cost-effective platform for the fabrication of perfectly ordered nanostructures on substrates for various applications in nanotechnology.

Adhesion Maturation of Neutrophils on Nanoscopically Presented Platelet Glycoprotein Ibα

Neutrophilic granulocytes play a fundamental role in cardiovascular disease. They interact with platelet aggregates via the integrin Mac-1 and the platelet receptor glycoprotein Ibα (GPIbα). In vivo, GPIbα presentation is highly variable under different physiological and pathophysiological conditions. Here, we quantitatively determined the conditions for neutrophil adhesion in a biomimetic in vitro system, which allowed precise adjustment of the spacings between human GPIbα presented on the nanoscale from 60 to 200 nm. Unlike most conventional nanopatterning approaches, this method provided control over the local receptor density (spacing) rather than just the global receptor density. Under physiological flow conditions, neutrophils required a minimum spacing of GPIbα molecules to successfully adhere. In contrast, under low-flow conditions, neutrophils adhered on all tested spacings with subtle but nonlinear differences in cell response, including spreading area, spreading kinetics, adhesion maturation, and mobility. Surprisingly, Mac-1-dependent neutrophil adhesion was very robust to GPIbα density variations up to 1 order of magnitude. This complex response map indicates that neutrophil adhesion under flow and adhesion maturation are differentially regulated by GPIbα density. Our study reveals how Mac-1/GPIbα interactions govern cell adhesion and how neutrophils process the number of available surface receptors on the nanoscale. In the future, such in vitro studies can be useful to determine optimum therapeutic ranges for targeting this interaction.

(Invited) Catalytic Surface Reactions during Nucleation and Growth of Atomic Layer Deposition of Noble Metals: A Case Study for Platinum

Atomic layer deposition (ALD) of noble metals has attracted much attention in recent years for the deposition of thin metal films, as well as for the synthesis of supported metallic nanoparticles. Noble metal surfaces and nanoparticles possess catalytic activity for dissociation of metalorganic precursor and O2 molecules, which has important consequences for the reaction mechanisms of ALD. In this work, a case study is presented with respect to the importance of catalytic surface reactions during the nucleation and growth of Pt ALD, which serves as a model system for the growth of other noble metals by ALD. It is illustrated that atomic level understanding of these processes is vital for the development of novel nanopatterning and nanoparticle synthesis approaches.

Flexible Approach to Sensors Arrays Nanopatterning for Real-Time Water Contaminants Monitoring Platform

This paper reports on the development of a flexible nanopatterning approach using the NanoeNablerTM to manufacture miniaturised sensor arrays platform for real-time water quality assessment. Traditionally biosensors are fabricated by lithography, screen printing, inkjet printing, spin-or deep-coating methods to immobilize the sensing element onto substrate pre-patterned with electrodes. NanoeNablerTM patterning method is benchmarked against other currently adapted approaches for cost-effective sensors arrays manufacture. Sensors measuring ~1 µm diameter or more can be patterned for further employment in molecularly imprinted polymer structures. Notably, the dimensions of the sensor depend on the fluid being patterned and on the interaction forces between the substrate and the patterning tool. Thus, careful selecting of patterning parameters is vital for repeatable and controlled manufacture of sensors to guarantee superior sensitivity. The reported nanopatterning method is capable of accurately placing attoliter to femtoliter volumes of liquids, including proteins and DNAs, onto any substrate, thus making it an ideal technology for biomedical sensors. A custom-made 1 cm2 silicon wafer with 48 interdigited electrodes sensor heads was used as a platform for the multi-sensor array with potential use in a wide range of real-time monitoring applications.

Preparation and characterization of fully separated gold nanowire arrays

We reported on the development of an unconventional approach for the physical synthesis of laterally ordered self-organized arrays of well-separated metallic nanowires supported on nanostructured dielectric templates. The method, combining nanoscale patterning of the polyethylene terephthalate substrate by polarized light of excimer laser with glancing angle deposition of the gold, provides an interesting alternative to lithography-based nanopatterning approaches. Separation of individual nanowires is manifested by anisotropy of their electrical properties. Focused ion beam equipped scanning electron microscopy analysis revealed that the resulting nanowires were organized in parallel arrays of approximately 2500 wires with an average length of about 1000μm and uniform width of about 150nm.

The fabrication of PLGA microvessel scaffolds with nano-patterned inner walls

Poly (lactic-co-glycolic acid) (PLGA) is one of the most commonly used biodegradable, biocompatible materials. Nanostructured PLGA has immense potential for application in tissue engineering. In this article we discuss a novel approach for the fabrication of PLGA microvessel scaffolds with nanostructured inner walls. In this novel nano-patterning approach, the thermal reflow technique is first adapted to fabricate a semi-cylindrical photoresist master mold. A thin film of titanium and a thin film of aluminum are sputtered in sequence on the semi-cylindrical microvessel network. Aluminum foil anodization is then executed to transform the aluminum thin film into a porous anodic aluminum oxide (AAO) film. During the casting process a PLGA solution is cast on the AAO film to build up semi-cylindrical PLGA microstructures with nanostructured inner walls after which inductive coupled plasma (ICP) is implemented to assist bonding of the two PLGA structures. The result is the building of a network of microchannels with nano-patterned inner walls. Bovine endothelial cells (BECs) are carefully cultured in the scaffold via semi-dynamic seeding for 7 days. Observations show that the BECs grew more separately in a nano-patterned microvessel scaffold than they did in a smooth surface scaffold.

Self-organized metal nanowire arrays with tunable optical anisotropy

Here we report on the development of an unconventional approach for the physical synthesis of laterally ordered self-organized arrays of metallic nanowires supported on nanostructured dielectric templates. The method, based on a combination of nanoscale patterning of the glass substrate by ion beam sputtering with shadow deposition of the metal nanoparticles, provides a viable alternative to time consuming serial nanopatterning approaches. Far-field optical characterization demonstrates that the nanowire arrays exhibit tunable anisotropic properties in the visible range due to the excitation of localized plasmon resonances.

Polymer nanofibers by soft lithography

The fabrication of polymeric fibers by soft lithography is demonstrated. Polyurethane, patterned by capillarity-induced molding with high-resolution elastomeric templates, forms mm-long fibers with a diameter below 0.3μm. The Young’s modulus of the fabricated structures, evaluated by force-distance scanning probe spectroscopy, has a value of 0.8MPa. This is an excellent example of nanostructures feasible by the combination of soft nanopatterning and high-resolution fabrication approaches for master templates, and particularly electron-beam lithography.