Controlled Anisotropic Wetting by Plasma Treatment for Directed Self-Assembly of High-χ Block Copolymers.

The directed self-assembly (DSA) of block copolymers (BCPs) is a promising next-generation lithography technique for high-resolution patterning. However, achieving lithographically applicable BCP organization such as out-of-plane lamellae requires proper tuning of interfacial energies between the BCP domains and the substrate, which remains difficult to address effectively and efficiently with high-χ BCPs. Here, we present the successful generation of anisotropic wetting by plasma treatment on patterned spin-on-carbon (SOC) substrates and its application to the DSA of a high-χ Si-containing material, poly(1,1-dimethylsilacyclobutane)-block-polystyrene (PDMSB-b-PS), with a 9 nm half pitch. Exposing the SOC substrate to different plasma chemistries promotes the vertical alignment of the PDMSB-b-PS lamellae within the trenches. In particular, a patterned substrate treated with HBr/O2 plasma gives both a neutral wetting at the bottom interface and a strong PS-affine wetting at the sidewalls of the SOC trenches to efficiently guide the vertical BCP lamellae. Furthermore, prolonged exposure to HBr/O2 plasma enables an adjustment of the trench width and an increased density of BCP lines on the substrate. Experimental observations are in agreement with a free energy configurational model developed to describe the system. These advances, which could be easily implemented in industry, could contribute to the wider adoption of self-assembly techniques in microelectronics, and beyond to applications such as metasurfaces, surface-enhanced Raman spectroscopy, and sensing technologies.

Optical Trapping and Fast Discrimination of Label-Free Bacteriophages at the Single Virion Level.

There is a recent resurgence of interest in phage therapy (the therapeutic use of bacterial viruses) as an approach to eliminating difficult-to-treat infections. However, existing approaches for therapeutic phage selection and virulence testing are time-consuming, host-dependent, and facing reproducibility issues. Here, this study presents an innovative approach wherein integrated resonant photonic crystal (PhC) cavities in silicon are used as optical nanotweezers for probing and manipulating single bacteria and single virions with low optical power. This study demonstrates that these nanocavities differentiate between a bacterium and a phage without labeling or specific surface bioreceptors. Furthermore, by tailoring the spatial extent of the resonant optical mode in the low-index medium, phage distinction across phenotypically distinct phage families is demonstrated. The work paves the road to the implementation of optical nanotweezers in phage therapy protocols.

Hierarchical Structure of Gold and Carbon Electrode for Bilirubin Oxidase-Biocathode.

Biofuel cells (BFCs) with enzymatic electrocatalysts have attracted significant attention, especially as power sources for wearable and implantable devices; however, the applications of BFCs are limited owing to the limited O2 supply. This can be addressed by using air-diffusion-type bilirubin oxidase (BOD) cathodes, and thus the further development of the hierarchical structure of porous electrodes with highly effective specific surface areas is critical. In this study, a porous layer of gold is deposited over magnesium-oxide-templated carbon (MgOC) to form BOD-based biocathodes for the oxygen reduction reaction (ORR). Porous gold structures are constructed via electrochemical deposition of gold via dynamic hydrogen bubble templating (DHBT). Hydrogen bubbles used as a template and controlled by the Coulomb number yield a porous gold structure during the electrochemical deposition process. The current density of the ORR catalyzed by BOD without a redox mediator on the gold-modified MgOC electrode was 1.3 times higher than that of the ORR on the MgOC electrode. Furthermore, the gold-deposited electrodes were modified with aromatic thiols containing negatively charged functional groups to improve the orientation of BOD on the electrode surface to facilitate efficient electron transfer at the heterogeneous surface, thereby achieving an ORR current of 12 mA cm-2 at pH 5 and 25 °C. These results suggest that DHBT is an efficient method for the fabrication of nanostructured electrodes that promote direct electron transfer with oxidoreductase enzymes.

Self-organization and dewetting kinetics in sub-10 nm diblock copolymer line/space lithography.

In this work, we investigated the self-assembly of a lamellar block copolymer (BCP) under different wetting conditions. We explored the influence of the chemical composition of under-layers and top-coats on the thin film stability, self-assembly kinetics and BCP domain orientation. Three different chemistries were chosen for these surface affinity modifiers and their composition was tuned in order to provide either neutral wetting (i.e. an out-of-plane lamellar structure), or affine wetting conditions (i.e. an in-plane lamellar structure) with respect to a sub-10 nm PS-b-PDMSB lamellar system. Using such controlled wetting configurations, the competition between the dewetting of the BCP layer and the self-organization kinetics was explored. We also evaluated the spreading parameter of the BCP films with respect to the configurations of surface-energy modifiers and demonstrated that BCP layers are intrinsically unstable to dewetting in a neutral configuration. Finally, the dewetting mechanisms were evaluated with respect to the different wetting configurations and we clearly observed that the rigidity of the top-coat is a key factor to delay BCP film instability.

Electrochemical Biosensing of Glucose Based on the Enzymatic Reduction of Glucose.

In this work, the enzyme aldehyde reductase, also known as aldose reductase, was synthesized and cloned from a human gene. Spectrophotometric measurements show that in presence of the nicotinamide adenine dinucleotide phosphate cofactor (NADPH), the aldehyde reductase catalyzed the reduction of glucose to sorbitol. Electrochemical measurements performed on an electrodeposited poly(methylene green)-modified gold electrode showed that in the presence of the enzyme aldehyde reductase, the electrocatalytic oxidation current of NADPH decreased drastically after the addition of glucose. These results demonstrate that aldehyde reductase is an enzyme that allows the construction of an efficient electrochemical glucose biosensor based on glucose reduction.

An Ultra-Thin Near-Perfect Absorber via Block Copolymer Engineered Metasurfaces.

Producing ultrathin light absorber layers is attractive towards the integration of lightweight planar components in electronic, photonic, and sensor devices. In this work, we report the experimental demonstration of a thin gold (Au) metallic metasurface with near-perfect visible absorption (∼95 %). Au nanoresonators possessing heights from 5 - 15 nm with sub-50 nm diameters were engineered by block copolymer (BCP) templating. The Au nanoresonators were fabricated on an alumina (Al2O3) spacer layer and a reflecting Au mirror, in a film-coupled nanoparticle design. The BCP nanopatterning strategy to produce desired heights of Au nanoresonators was tailored to achieve near-perfect absorption at ≈ 600 nm. The experimental insight described in this work is a step forward towards realizing large area flat optics applications derived from subwavelength-thin metasurfaces.

Dry-Etching Processes for High-Aspect-Ratio Features with Sub-10 nm Resolution High-χ Block Copolymers.

Directed self-assembly of block copolymers (BCP) is a very attractive technique for the realization of functional nanostructures at high resolution. In this work, we developed full dry-etching strategies for BCP nanolithography using an 18 nm pitch lamellar silicon-containing block copolymer. Both an oxidizing Ar/O2 plasma and a nonoxidizing H2/N2 plasma are used to remove the topcoat material of our BCP stack and reveal the perpendicular lamellae. Under Ar/O2 plasma, an interfacial layer stops the etch process at the topcoat/BCP interface, which provides an etch-stop but also requires an additional CF4-based breakthrough plasma for further etching. This interfacial layer is not present in H2/N2. Increasing the H2/N2 ratio leads to more profound modifications of the silicon-containing lamellae, for which a chemistry in He/N2/O2 rather than Ar/O2 plasma produces a smoother and more regular lithographic mask. Finally, these features are successfully transferred into silicon, silicon-on-insulator, and silicon nitride substrates. This work highlights the performance of a silicon-containing block copolymer at 18 nm pitch to pattern relevant hard-mask materials for various applications, including microelectronics.

Phage susceptibility testing and infectious titer determination through wide-field lensless monitoring of phage plaque growth.

The growing number of drug-resistant bacterial infections worldwide is driving renewed interest in phage therapy. Based on the use of a personalized cocktail composed of highly specific bacterial viruses, this therapy relies on a range of tests on agar media to determine the most active phage on a given bacterial target (phage susceptibility testing), or to isolate new lytic phages from an environmental sample (enrichment of phage banks). However, these culture-based techniques are still solely interpreted through direct visual detection of plaques. The main objective of this work is to investigate computer-assisted methods in order to ease and accelerate diagnosis in phage therapy but also to study phage plaque growth kinetics. For this purpose, we designed a custom wide-field lensless imaging device, which allows continuous monitoring over a very large area sensor (3.3 cm2). Here we report bacterial susceptibility to Staphylococcus aureus phage in 3 hr and estimation of infectious titer in 8 hr 20 min. These are much shorter time-to-results than the 12 to 24 hours traditionally needed, since naked eye observation and counting of phage plaques is still the most widely used technique for susceptibility testing prior to phage therapy. Moreover, the continuous monitoring of the samples enables the study of plaque growth kinetics, which enables a deeper understanding of the interaction between phage and bacteria. Finally, thanks to the 4.3 µm resolution, we detect phage-resistant bacterial microcolonies of Klebsiella pneumoniae inside the boundaries of phage plaques and thus show that our prototype is also a suitable device to track phage resistance. Lensless imaging is therefore an all-in-one method that could easily be implemented in cost-effective and compact devices in phage laboratories to help with phage therapy diagnosis.

Lithographically Defined Cross-Linkable Top Coats for Nanomanufacturing with High-χ Block Copolymers.

The directed self-assembly (DSA) of block copolymers (BCPs) is a powerful method for the manufacture of high-resolution features. Critical issues remain to be addressed for successful implementation of DSA, such as dewetting and controlled orientation of BCP domains through physicochemical manipulations at the BCP interfaces, and the spatial positioning and registration of the BCP features. Here, we introduce novel top-coat (TC) materials designed to undergo cross-linking reactions triggered by thermal or photoactivation processes. The cross-linked TC layer with adjusted composition induces a mechanical confinement of the BCP layer, suppressing its dewetting while promoting perpendicular orientation of BCP domains. The selection of areas of interest with perpendicular features is performed directly on the patternable TC layer via a lithography step and leverages attractive integration pathways for the generation of locally controlled BCP patterns and nanostructured BCP multilayers.

Nanopatterning via Self-Assembly of a Lamellar-Forming Polystyrene-block-Poly(dimethylsiloxane) Diblock Copolymer on Topographical Substrates Fabricated by Nanoimprint Lithography.

The self-assembly of a lamellar-forming polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer (DBCP) was studied herein for surface nanopatterning. The DBCP was synthesized by sequential living anionic polymerization of styrene and hexamethylcyclotrisiloxane (D3). The number average molecular weight (Mn), polydispersity index (Mw/Mn) and PS volume fraction (φps) of the DBCP were MnPS = 23.0 kg mol-1, MnPDMS = 15.0 kg mol-1, Mw/Mn = 1.06 and φps = 0.6. Thin films of the DBCP were cast and solvent annealed on topographically patterned polyhedral oligomeric silsesquioxane (POSS) substrates. The lamellae repeat distance or pitch (λL) and the width of the PDMS features (dL) are ~35 nm and ~17 nm, respectively, as determined by SEM. The chemistry of the POSS substrates was tuned, and the effects on the self-assembly of the DBCP noted. The PDMS nanopatterns were used as etching mask in order to transfer the DBCP pattern to underlying silicon substrate by a complex plasma etch process yielding sub-15 nm silicon features.

Straightforward Integration Flow of a Silicon-Containing Block Copolymer for Line-Space Patterning.

A promising alternative for the next-generation lithography is based on the directed self-assembly of block copolymers (BCPs) used as a bottom-up tool for the definition of nanometric features. Herein, a straightforward integration flow for line-space patterning is reported for a silicon BCP system, that is, poly(1,1-dimethylsilacyclobutane)-b-poly(styrene) (PDMSB-b-PS), able to define sub 15 nm features. Both in-plane cylindrical (L0 = 20.7 nm) and out-of-plane lamellar structures (L0 = 23.2 nm) formed through a rapid thermal annealing-10 min at 180 °C-were successfully integrated using graphoepitaxy to provide a long-range ordering of the BCP structure without the use of underlayers or top coats. Subsequent deep transfer into the silicon substrate using the hardened oxidized PDMSB domains as a mask is demonstrated. Combining a rapid self-assembly behavior, straightforward integration, and an excellent etching contrast, PDMSB-b-PS may become a material of choice for the next-generation lithography.

Sub-10 nm Silicon Nanopillar Fabrication Using Fast and Brushless Thermal Assembly of PS-b-PDMS Diblock Copolymer.

A new approach to obtaining spherical nanodomains using polystyrene-block-polydimethylsiloxane (PS-b-PDMS) is proposed. To reduce drastically the process time, we blended a copolymer with cylindrical morphology with a PS homopolymer. Adding PS homopolymer into a low-molar-mass cylindrical morphology PS-b-PDMS system drives it toward a spherical morphology. Besides, by controlling the as-spun state, spherical PDMS nanodomains could be kept and thermally arranged. This PS-homopolymer addition allows not only an efficient, purely thermal arrangement process of spheres but also the ability to work directly on nontreated silicon substrates. Indeed, as shown by STEM measurements, no PS brush surface treatment was necessary in our study to avoid a PDMS wetting layer at the interface with the Si substrate. Our approach was compared to a sphere-forming diblock copolymer, which needs a longer thermal annealing. Furthermore, GISAXS measurements provided complete information on PDMS sphere features. Excellent long-range order spherical microdomains were therefore produced on flat surfaces and inside graphoepitaxy trenches with a period of 21 nm, as were in-plane spheres with a diameter of 8 nm with a 15 min thermal annealing. Finally, direct plasma-etching transfer into the silicon substrate was demonstrated, and 20 nm high silicon nanopillars were obtained, which are very promising results for various nanopatterning applications.

Pulsed transfer etching of PS-PDMS block copolymers self-assembled in 193 nm lithography stacks.

This work presents the graphoepitaxy of high-χ block copolymers (BCP) in standard industry-like lithography stacks and their transfer into the silicon substrate The process includes conventional 193 nm photolithography, directed self-assembly of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and pulsed plasma etching to transfer the obtained features into the substrate. PS-b-PDMS has a high Flory-Huggins interaction parameter (high-χ) and is capable of achieving sub-10 nm feature sizes. The photolithography stack is fabricated on 300 mm diameter silicon wafers and is composed of three layers: spin-on-carbon (SoC), silicon-containing anti-reflective coating (SiARC) and 193 nm photolithography resist. Sixty-nanometer-deep trenches are first patterned by plasma etching in the SiARC/SoC stack using the resist mask. The PS-b-PDMS is then spread on the substrate surface. Directed self-assembly (DSA) of the BCP is induced by a solvent vapor annealing process and PDMS cylinders parallel to the substrate surface are obtained. The surface chemistry based on SoC permits an efficient etching process into the underlying silicon substrate. The etching process is performed under dedicated pulsed plasma etching conditions. Fifteen nanometer half-pitch dense line/space features are obtained with a height up to 90 nm.

Order quantification of hexagonal periodic arrays fabricated by in situ solvent-assisted nanoimprint lithography of block copolymers.

Directed self-assembly of block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO) thin film was achieved by a one-pot methodology of solvent vapor assisted nanoimprint lithography (SAIL). Simultaneous solvent-anneal and imprinting of a PS-b-PEO thin film on silicon without surface pre-treatments yielded a 250 nm line grating decorated with 20 nm diameter nanodots array over a large surface area of up to 4' wafer scale. The grazing-incidence small-angle x-ray scattering diffraction pattern showed the fidelity of the NIL stamp pattern replication and confirmed the periodicity of the BCP of 40 nm. The order of the hexagonally arranged nanodot lattice was quantified by SEM image analysis using the opposite partner method and compared to conventionally solvent-annealed block copolymer films. The imprint-based SAIL methodology thus demonstrated an improvement in ordering of the nanodot lattice of up to 50%, and allows significant time and cost reduction in the processing of these structures.

Local reorganization of diblock copolymer domains in directed self-assembly monitored by in situ high-temperature AFM.

In situ high-temperature AFM was used to locally follow dynamic processes, leading to directed self-assembly of copolymers in the context of graphoepitaxy. We focused on the effect of heating for temperatures much higher than the Tg of the used PS-b-PMMA polymer. We showed that such conditions favors the block rearrangement, leading to very regular and perfectly aligned structures in limited times. The use of in situ AFM allowed us to locally investigate the self-organization process at high temperature, thus bringing new insights into self-assembly of block copolymers by graphoepitaxy. In particular, we demonstrate that a slight increase of temperature between 180 and 200 °C allowed overpassing an energy barrier and considerably improves the long distance arrangement, even for relatively short times.

Highly organised and dense vertical silicon nanowire arrays grown in porous alumina template on <100> silicon wafers.

In this work, nanoimprint lithography combined with standard anodization etching is used to make perfectly organised triangular arrays of vertical cylindrical alumina nanopores onto standard <100>-oriented silicon wafers. Both the pore diameter and the period of alumina porous array are well controlled and can be tuned: the periods vary from 80 to 460 nm, and the diameters vary from 15 nm to any required diameter. These porous thin layers are then successfully used as templates for the guided epitaxial growth of organised mono-crystalline silicon nanowire arrays in a chemical vapour deposition chamber. We report the densities of silicon nanowires up to 9 × 109 cm-2 organised in highly regular arrays with excellent diameter distribution. All process steps are demonstrated on surfaces up to 2 × 2 cm2. Specific emphasis was made to select techniques compatible with microelectronic fabrication standards, adaptable to large surface samples and with a reasonable cost. Achievements made in the quality of the porous alumina array, therefore on the silicon nanowire array, widen the number of potential applications for this technology, such as optical detectors or biological sensors.

Surface-directed dewetting of a block copolymer for fabricating highly uniform nanostructured microdroplets and concentric nanorings.

Through a combination of nanoimprint lithography and block copolymer self-assembly, a highly regular dewetting process of a symmetric diblock copolymer occurs whereby the hierarchal formation of microdroplets and concentric nanorings emerges. The process is driven by the unique chemical properties and geometrical layout of the underlying patterned silsesquioxane micrometer-sized templates. Given the presence of nonpreferential substrate-polymer interactions, directed dewetting was utilized to produce uniform arrays of microsized droplets of microphase separated polystyrene-block-poly(methyl methylacrylate) (PS-b-PMMA), following thermal annealing at 180 °C. Microdroplets with diameters greater than 400 nm exhibited a hexagonal close-packed arrangement of nanodots on the surface with polydomain ordering. At the droplet periphery, the polydomain ordering was severely disrupted because of a higher in-plane radius of curvature. By reducing the droplet size, the in-plane radius of curvature of the microdroplet becomes significant and the PMMA cylinders adopt parallel structures in this confined geometry. Continuous scaling of the droplet results in the generation of isolated, freestanding, self-aligned, and self-supported oblique nanorings (long axis ∼250-350 nm), which form as interstitial droplets between the larger microdroplets. Optical and magnetic-based nanostructures may benefit from such hierarchal organization and self-supporting/aligned nanoring templates by combining more than one lithography technique with different resolution capabilities.