Search

Increasing the surface area-to-volume ratio of materials through size reduction is a desired approach to access maximum possible surface sites in applications such as catalysis. However, increase in the surface energy with the decrease in dimension warrants strong ligands to stabilize nanosystems, which mask the accessibility of the active surface sites. Owing to this, the realization of the true potential of a catalyst's surface remains challenging. Here, we employed a rationally designed strategy to synthesize infant Au nanoclusters—that alleviates the requirement of any separate ligand removal step—to unleash their actual potential to register a record high maximum turn-over frequency (TOFmax) of 72 900 h−1 and 65 500 h−1 in the benchmark catalytic reduction of 4-nitrophenol and catalytic H2 generation from an ammonia borane–sodium borohydride mixture, respectively. Such a phenomenal catalytic activity has been realized via the synthesis and stabilization of Au nanoclusters using solid citric acid and a super-concentrated aqueous AuCl3 solution, a pathway entirely different from the conventional modifications of the Turkevich and Brust methods. The crux of the synthetic strategy lies in precise control of the water content and thereby ensuring that the final Au nanoclusters remain in the solid state. During the synthesis, citric acid not only acts as a reducing agent to yield ‘infant’ Au nanoclusters but also provides a barrier matrix to arrest their growth. In solution, its weak capping ability and rapid dissolution allows the reactants to easily access the active sites of Au nanoclusters, thus leading to faster catalysis. Our study reveals that the true potential of metal nanoclusters as catalysts is actually far higher than what has been reported in the literature.

Direct patterning of thermoelectric metal chalcogenides can be challenging and is normally constrained to certain geometries and sizes. Here we report the synthesis, characterization, and direct writing of sub-10 nm wide bismuth sulfide (Bi2S3) using a single-source, spin-coatable, and electron-beam-sensitive bismuth(III) ethylxanthate precursor. In order to increase the intrinsically low carrier concentration of pristine Bi2S3, we developed a self-doping methodology in which sulfur vacancies are manipulated by tuning the temperature during vacuum annealing, to produce an electron-rich thermoelectric material. We report a room-temperature electrical conductivity of 6 S m–1 and a Seebeck coefficient of −21.41 μV K–1 for a directly patterned, substoichiometric Bi2S3 thin film. We expect that our demonstration of directly writable thermoelectric films, with further optimization of structure and morphology, can be useful for on-chip applications.

Tailoring writability and obtaining better signal-to-noise ratio performance by tuning the magnetic and microstructural properties of FePt media is of great interest in the bid to achieve high areal densities for next generation hard disk drives (HDDs). Conventional ways to tune FePt media are primarily by either the insertion of additional layers, or by inclusion of segregants such as B, C, Ni, SiO2 etc. Here we describe an approach that involves modifying growth kinetics by N inclusion, via plasma treatment in FePt bilayers (consisting of a hard and a soft FePt layer). The soft FePt layer aids in obtaining easy writability, while nitrogen plasma treatment of the interface of the two FePt layers facilitates suitable tailoring of the microstructure. This approach contributed to lowering of grain dimension as well as reduction in domain sizes in the FePt bilayers, but with the unwanted side-effects of reduction in squareness and ordering. However, we further propose a method to alleviate these concerns by the deposition of the soft FePt layer in partial nitrogen atmosphere, that restored the squareness and ordering while retaining the smaller domains obtained by nitrogen plasma treatment. Thus, the proposed approach provides a potential direction towards meeting the mutually conflicting requirements of easy writability and better signal-to-noise ratio performance in FePt media. ASTAR (Agency for Sci., Tech. and Research, S’pore) Accepted version

UV-nanoimprint lithography (UV-NIL) is a promising technique for direct fabrication of functional oxide nanostructures. Since it is mostly carried out in aerobic conditions, the free radical polymerization during imprinting is retarded due to the radical scavenging ability of oxygen. Therefore, it is highly desirable to have an oxygen-insensitive photo-curable resin that not only alleviates the requirement of inert conditions but also enables patterning without making substantial changes in the process. Here we demonstrate the formulation of metal-containing resins that employ oxygen-insensitive thiol–ene photo-click chemistry. Allyl acetoacetate (AAAc) has been used as a bifunctional monomer that, on one hand, chelates with the metal ion, and on the other hand, offers a reactive alkene group for polymerization. Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), a four-arm thiol derivative, is used as a crosslinker as well as an active component in the thiol–ene photo-click chemistry. The FT-IR analyses on the metal-free and metal-containing resin formulations revealed that the optimum ratio of alkene to thiol is 1 : 0.5 for an efficient photo-click chemistry. The thiol–ene photo-click chemistry has been successfully demonstrated for direct imprinting of oxides by employing TiO2 and Ta2O5 as candidate systems. The imprinted films of metal-containing resins were subjected to calcination to obtain the corresponding patterned metal oxides. This technique can potentially be expanded to other oxide systems as well.

Direct imprinting of metals is predominantly achieved by using polydimethylsiloxane (PDMS) molds to pattern metal nanoparticles and subsequently melting them to form continuous structures. Although such a combination can successfully imprint metals, the yield and reproducibility are usually low when sub-100 nm features over large areas are desired. In this work, we demonstrate a simple method involving the addition of a cross-linker ethylene glycol dimethacrylate (EDMA) to a palladium metal precursor, and its in situ free radical polymerization during imprinting, which not only dramatically increases the yield to ∼100% but also enables high reproducibility. Palladium mercaptide resist was formed by dissolving acetoxy(benzylthio)palladium, EDMA and azobis-(isobutyronitrile) in an organic solvent mixture. The resist underwent polymerization when imprinted using a silicon mold at 120 °C with pressures as low as 30 bar. Polymerization rigidly shapes the imprinted patterns, traps the metal atoms, reduces the surface energy and strengthens the structures, thereby giving ∼100% yield after demolding. Heat-treatment of the imprinted structures at 330 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to palladium nanostructures as small as ∼35 nm wide, over areas >1 cm × 1 cm. With suitable precursors, our technique can potentially be extended to pattern noble metals such as platinum, gold and silver.

The photocatalytic self-cleaning characteristics of titania facilitate the fabrication of reuseable templates for protein nanopatterning. Titania nanostructures were fabricated over square centimeter areas by interferometric lithography (IL) and nanoimprint lithography (NIL). With the use of a Lloyd's mirror two-beam interferometer, self-assembled monolayers of alkylphosphonates adsorbed on the native oxide of a Ti film were patterned by photocatalytic nanolithography. In regions exposed to a maximum in the interferogram, the monolayer was removed by photocatalytic oxidation. In regions exposed to an intensity minimum, the monolayer remained intact. After exposure, the sample was etched in piranha solution to yield Ti nanostructures with widths as small as 30 nm. NIL was performed by using a silicon stamp to imprint a spin-cast film of titanium dioxide resin; after calcination and reactive ion etching, TiO2 nanopillars were formed. For both fabrication techniques, subsequent adsorption of an oligo(ethylene glycol) functionalized trichlorosilane yielded an entirely passive, protein-resistant surface. Near-UV exposure caused removal of this protein-resistant film from the titania regions by photocatalytic degradation, leaving the passivating silane film intact on the silicon dioxide regions. Proteins labeled with fluorescent dyes were adsorbed to the titanium dioxide regions, yielding nanopatterns with bright fluorescence. Subsequent near-UV irradiation of the samples removed the protein from the titanium dioxide nanostructures by photocatalytic degradation facilitating the adsorption of a different protein. The process was repeated multiple times. These simple methods appear to yield durable, reuseable samples that may be of value to laboratories that require nanostructured biological interfaces but do not have access to the infrastructure required for nanofabrication.

The fabrication of very narrow metal lines by the lift-off technique, especially below sub-10 nm, is challenging due to thinner resist requirements in order to achieve the lithographic resolution. At such small length scales, when the grain size becomes comparable with the line-width, the built-in stress in the metal film can cause a break to occur at a grain boundary. Moreover, the line-width roughness (LWR) from the patterned resist can result in deposited metal lines with a very high LWR, leading to an adverse change in device characteristics. Here a new approach that is not based on the lift-off technique but rather on low temperature hydrogen reduction ofelectron-beam patterned metal naphthenates is demonstrated. This not only enables the fabrication of sub-10 nm metal lines of good integrity, but also of low LWR, below the limit of 3.2 nm discussed in the International Technology Roadmap for Semiconductors. Using this method, sub-10 nm nickel wires are obtained by reducing patterned nickel naphthenate lines in a hydrogen-rich atmosphere at 500°C for 1 h. The LWR (i.e., 3 σ LWR ) of these nickel nanolines was found to be 2.9 nm. The technique is general and is likely to be suitable for fabrication of nanostructures of most commonly used metals (and their alloys), such as iron, cobalt, nickel, copper, tungsten, molybdenum, and so on, from their respective metal―organic compounds.

L10 FePtC granular media are being studied as potential future magnetic recording media and are set to be used in conjunction with heat assisted magnetic recording (HAMR) to enable recording at write fields within the range of current day recording heads. Media structures based on a FePtC storage layer and a capping layer can alleviate the switching field distribution (SFD) requirements of HAMR and reduce the noise originating from the writing process. However, the current designs suffer from SFD issues due to high temperature writing. To overcome this problem, we study a CoPt/FePtC exchange coupled composite structure, where FePtC serves as the storage layer and CoPt (with higher Curie temperature, Tc) as the capping layer. CoPt remains ferromagnetic at near Tc of FePtC. Consequently, the counter exchange energy from CoPt would reduce the noise resulting from the adjacent grain interactions during the writing process. CoPt/FePtC bilayer samples with different thicknesses of CoPt were investigated. Our studies found that CoPt forms a continuous layer at a thickness of 6 nm and leads to considerable reduction in the saturation field and its distribution. ASTAR (Agency for Sci., Tech. and Research, S’pore) Published version

Conventional patterning of HfO2 as a gate dielectric is a multistep complicated process that involves deposition of oxide, photolithography, and hard mask etching. In order to simplify the process of HfO2 patterning, the authors have developed photo- and electron beam-sensitive spin-coatable HfO2 resists for direct writing. They were prepared by reacting hafnium tert-butoxide with benzoylacetone in n-butanol and were found to be highly stable in air. Fourier transform infrared studies suggest that exposure to radiation results in the gradual removal of organic material from the resist and the enrichment of the resist with inorganics. This makes the exposed resist insoluble in organic solvents such as ethanol, thereby providing high-resolution negative patterns as small as ∼10nm wide. A silicon-on-insulator field effect transistor has been fabricated using sol-gel-derived HfO2 resist as a high-k gate dielectric and characterized over a range of temperatures. At room temperature a relatively high gate leaka...

Assessment of the microbial safety of water resources is among the most critical issues in global water safety. As the current detection methods have limitations such as high cost and long process time, new detection techniques have transpired among which microfluidics is the most attractive alternative. Here, we show a novel hybrid dielectrophoretic (DEP) system to separate and detect two common waterborne pathogens, Escherichia coli (E. coli), a bacterium, and Cryptosporidium parvum (C. parvum), a protozoan parasite, from water. The hybrid DEP system integrates a chemical surface coating with a microfluidic device containing inter-digitated microelectrodes to impart positive dielectrophoresis for enhanced trapping of the cells. Trimethoxy(3,3,3-trifluoropropyl) silane, (3-aminopropyl)triethoxysilane, and polydiallyl dimethyl ammonium chloride (p-DADMAC) were used as surface coatings. Static cell adhesion tests showed that among these coatings, the p-DADMAC-coated glass surface provided the most effective cell adhesion for both the pathogens. This was attributed to the positively charged p-DADMAC-coated surface interacting electrostatically with the negatively charged cells suspended in water leading to increased cell trapping efficiency. The trapping efficiency of E. coli and C. parvum increased from 29.0% and 61.3% in an uncoated DEP system to 51.9% and 82.2% in the hybrid DEP system, respectively. The hybrid system improved the cell trapping by encouraging the formation of cell pearl-chaining. The increment in trapping efficiency in the hybrid DEP system was achieved at an optimal frequency of 1 MHz and voltage of 2.5 Vpp for C. parvum and 2 Vpp for E. coli, the latter is lower than 2.5 Vpp and 7 Vpp, respectively, utilized for obtaining similar efficiency in an uncoated DEP system.

Tuning the magnetic properties of FePt media is of great interest in the bid to achieve high areal densities. In this work, we demonstrate that properties of FePt media can be tuned using a two-step temperature deposited FePt bilayer. In this bilayer scheme, the first layer of FePt was deposited at a high nominal temperature (600 °C), whilst the second layer was deposited at a lower temperature over the first layer. This resulted in tunable magnetic and improved topographical properties, and was due to the interplay of a number of temperature-dependent factors such as epitaxial growth, new grain nucleation, surface mobility, and difference in the thermal expansion coefficients. Transmission electron microscopy imaging was used to understand the growth dynamics of the second FePt layer in the two-step temperature deposited structures. Accepted version

Electron beam-sensitive spin-coatable Al2O3 resists were prepared by chemically modifying aluminium tri-sec-butoxide with various β-ketoesters (R-acetoacetates, R = methyl, ethyl, isopropyl, isobutyl, isoamyl, heptyl, benzyl and 2-[methacryloyloxy] ethyl) in isopropyl alcohol. The reaction product was a chelated complex. With increasing molecular weight of R, there was an increase in electron beam sensitivity of spin-coatable Al2O3 resists. This appears to be due to decreased stability of the chelated complex formed by higher molecular weight R-acetoacetates. Fourier transform infrared (FTIR) spectroscopy studies indicate that exposure to an electron beam results in the breakdown of chelate rings, making the exposed area insoluble during development. Electron beam nanolithography produced 8 nm wide lines. These are the smallest oxide lines written using a sol-gel-based resist.

Satisfying the mutually conflicting requirements of easy switchability and high thermal stability still remains a hindrance to achieving ultra-high areal densities in hard disk drives. Exchange coupled composite media used with proper exchange control layers (ECLs) presents a potential solution to circumvent this hindrance. In this work, we have studied the role of MgO and Ta ECLs of different thicknesses in reducing the switching field of FePt media. MgO ECL was found to be more effective than a Ta ECL. For a 2 nm MgO ECL, the switching field could be reduced by 41% and at the cost of only a limited loss in thermal stability. Furthermore, a very high switching efficiency of 1.9 was obtained using 2 nm MgO ECL. So, with a proper choice of ECL material and thickness, the switching field of FePt media can be substantially reduced while ensuring high thermal stability and a better signal-to-noise ratio, thus potentially paving the way for very high areal density media. NRF (Natl Research Foundation, S’pore) ASTAR (Agency for Sci., Tech. and Research, S’pore) Published version

Three-dimensional hierarchical patterning of metals is of paramount importance in diverse fields involving photonics, controlling surface wettability and wearable electronics. Conventionally, this type of structuring is tedious and usually involves layer-by-layer lithographic patterning. Here, we describe a simple process of direct nanoimprint lithography using palladium benzylthiolate, a versatile metal-organic ink, which not only leads to the formation of hierarchical patterns but also is amenable to layer-by-layer stacking of the metal over large areas. The key to achieving such multi-faceted patterning is hysteretic melting of ink, enabling its shaping. It undergoes transformation to metallic palladium under gentle thermal conditions without affecting the integrity of the hierarchical patterns on micro- as well as nanoscale. A metallic rice leaf structure showing anisotropic wetting behavior and woodpile-like structures were thus fabricated. Furthermore, this method is extendable for transferring imprinted structures to a flexible substrate to make them robust enough to sustain numerous bending cycles.

Self-assembly of block copolymers has been identified as a potential candidate for high density fabrication of nanostructures. However, the factors affecting its reliability and reproducibility as a patterning technique on various kinds of surfaces are not well-established. Studies pertaining to block copolymer self-assembly have been confined to ultra-flat substrates without taking into consideration the effect of surface roughness. Here, we show that a slight change in the angstrom-scale roughness arising from the surface of a material creates a profound effect on the self-assembly of polystyrene-polydimethylsiloxane block copolymer. Its self-assembly was found to be dependent on both the root mean square roughness (R(rms)) of the surface and the type of solvent annealing system used. It was observed that surface with R(rms)5.0 Å showed self-assembly. Above this value, the kinetic hindrance posed by the surface roughness on the block copolymer leads to its conforming to the surface without observable phase separation.

After the cost of ownership of tool, the next significant cost involved in nanoimprint lithography is that of mold fabrication. The cost of mold fabrication is proportional to the area of pattern and follows an inverse relationship with the pattern resolution. In this work, the authors demonstrate proof-of-concept fabrication of Si and SiO2 grating molds of variable feature sizes, spacings, densities, and aspect ratios that can be generated from a single Si master mold of 2 μm line and space features. This process utilizes “SiO2 resin,” which can be imprinted via in situ thermal free radical polymerization. Heat-treatment of the patterned resin resulted in loss of organics, formation of SiOx and gave rise to known feature size reduction (∼65%). After the pattern transfer using SiOx as the etch mask, a Si daughter mold containing 0.7 μm wide gratings with 3.3 μm spacing was generated. The process of imprinting and heat-treatment was repeated using the daughter mold, which regenerated a mold that approximates the master mold feature profile. Our technique demonstrates that submicron-sized features can be achieved from Si molds containing micron-sized features and vice versa. Such flexibility may lead to substantial reduction in the cost of mold fabrication.

We report the self-assembly of single crystals of single-walled carbon nanotubes (SWCNTs) using thermolysis of nano-patterned precursors. The synthesis of these perfectly ordered, single crystals of SWCNTs results in extended structures with dimension on the micrometer scale. Each crystal is composed of an ordered array of tubes with identical diameters and chirality, although these properties vary between crystals. The results show that SWCNTs can be produced as a perfect bulk material on the micrometer scale and point toward the synthesis of bulk macroscopic crystalline material.

Multiple mixed interfaces and a critical carbon thickness in sub-10-nm overcoats are essential for low wear and friction., Friction and wear cause energy wastage and system failure. Usually, thicker overcoats serve to combat such tribological concerns, but in many contact sliding systems, their large thickness hinders active components of the systems, degrades functionality, and constitutes a major barrier for technological developments. While sub-10-nm overcoats are of key interest, traditional overcoats suffer from rapid wear and degradation at this thickness regime. Using an enhanced atomic intermixing approach, we develop a ~7- to 8-nm-thick carbon/silicon nitride (C/SiNx) multilayer overcoat demonstrating extremely high wear resistance and low friction at all tribological length scales, yielding ~2 to 10 times better macroscale wear durability than previously reported thicker (~20 to 100 nm) overcoats on tape drive heads. We report the discovery of many fundamental parameters that govern contact sliding and reveal how tuning atomic intermixing at interfaces and varying carbon and SiNx thicknesses strongly affect friction and wear, which are crucial for advancing numerous technologies.