Nickel nanoparticles and nanowires obtained by scanning probe lithography using point indentation technique

A lithographic method of obtaining metal nanowires and nanoparticles on solid substrates is proposed, which employs a polymer mask with windows for the metal deposition formed by indentation in an atomic force microscope. Using this method, Ni nanowires with a minimum width of 60 nm, thicknesses within 6?C20 nm, and lengths up to 20 ??m and Ni nanoparticles with a preset ordered arrangement have been obtained on a SiO₂ surface. The domain structure in obtained nanoobjects has been studied by the magnetic force microscopy technique.     

Application of scanning probe lithography to graphite patterning

We applied the scanning probe lithographic technique to a graphite patterning in air and analyzed the patterned sample with the lateral force microscopy and Raman spectroscopy. The local electric field generated from a tip caused either etching or oxidization depending on the electric field intensity in air. We have found that the frictional force between the tip and local oxidized graphite surface was increased remarkably from lateral force analysis. Also, it was found that the graphene layer was peeled from the graphite surface in the etching process, which could be a potential tool as a top-down nano-fabrication process for the graphene nano device without contamination.     

Non-lift-off block copolymer lithography of 25 nm magnetic nanodot arrays

Although nanolithographic techniques based on self-assembled block copolymer templates offer tremendous potential for fabrication of large-area nanostructure arrays, significant difficulties arise with both the lift-off and etch processes typically used for pattern transfer. These become progressively more important in the limit of extreme feature sizes. The few techniques that have been developed to avoid these issues are quite complex. Here, we demonstrate successful execution of a nanolithographic process based on solvent annealed, cylinder-forming, easily degradable, polystyrene-b-polylactide block copolymer films that completely avoids lift-off in addition to the most challenging aspects of etching. We report a "Damascene-type" process that overfills the polystyrene template with magnetic metal, employs ion beam milling to planarize the metal surface down to the underlying polystyrene template, then exploits the large etch rate contrast between polystyrene and typical metals to generate pattern reversal of the original template into the magnetic metal. The process is demonstrated via formation of a large-area array of 25 nm diameter ferromagnetic Ni(80)Fe(20) nanodots with hexagonally close-packed order. Extensive microscopy, magnetometry, and electrical measurements provide detailed characterization of the pattern formation. We argue that the approach is generalizable to a wide variety of materials, is scalable to smaller feature sizes, and critically, minimizes etch damage, thus preserving the essential functionality of the patterned material.     

Conductive polymer patterned media fabricated by diblock copolymer lithography for scanning multiprobe data storage

A conductive polymer dot pattern has been fabricated as a patterned medium using diblock copolymer lithography (DCL) for scanning multiprobe data storage systems (SMDSSs). DCL can easily provide a higher dots pattern density than that obtained using electron beam lithography. For DCL, the microphase-separated structure of polystyrene-block-polymethylmethacrylate is utilized. Then, the closed dot pattern of polyaniline (PANI) with a center to center distance of adjacent dots of 30?nm is fabricated by DCL. Electrical modification experiments of the fabricated PANI dots are demonstrated using scanning probe microscopy (SPM). As a result, the conductivities of the modified dots are selectively changed by applying modification voltages with the tip of the SPM probe. Recording on the conductive polymer with 30?nm pitch at the minimum can be demonstrated, which corresponds to a recording density of ～700?Gbits?inch(-2). These results show that the conductive polymer patterned medium has the potential ability to achieve high-density recording for SMDSSs.     

Ordered binary arrays of Au nanoparticles derived from colloidal lithography

By using angle-resolved colloidal lithography and O2-plasma etched bilayers of hexagonally packed spheres as templates, we succeeded in fabrication of highly ordered binary arrays of gold nanoparticles with varied shapes, for instance, with a shuttlecock-like shape composed of a small crescent-shaped nanoparticle and a big fan-shaped one. The size and shape of both small and big nanoparticles obtained were manipulated by the plasma etching period and the incidence angle of Au vapor flow. The subsequent thermal annealing led to binary arrays of round Au nanoparticles with a rather narrow distribution in terms of size and shape. Our approach should pave a simple and versatile colloidal way to form binary nanoparticle arrays, holding immense promise for technical applications such as nanoelectronics and nanophotonics.     

Nanowire conductive polymer gas sensor patterned using self-assembled block copolymer lithography

Nanostructured conjugated organic thin films are essential building blocks for highly integrated organic devices. We demonstrate the large-area fabrication of an array of well-ordered 15 nm wide conducting polymer nanowires by using an etch mask consisting of self-assembled patterns of cylinder-forming poly(styrene-b-dimethylsiloxane) diblock copolymer confined in topographic templates. The poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) nanowires operated as an ethanol vapor sensor, suggesting that the electronic properties of the organic film were preserved during the patterning processes. The higher sensitivity to ethanol vapor, compared to an unpatterned film with the same thickness, was attributed to the enhanced surface-to-volume ratio of the nanowire array.     

Mussel-inspired block copolymer lithography for low surface energy materials of teflon, graphene, and gold

Mussel-inspired interfacial engineering is synergistically integrated with block copolymer (BCP) lithography for the surface nanopatterning of low surface energy substrate materials, including, Teflon, graphene, and gold. The image shows the Teflon nanowires and their excellent superhydrophobicity.     

The fabrication of tunable nanoporous oxide surfaces by block copolymer lithography and atomic layer deposition

Patterned nanoscale materials with controllable characteristic feature sizes and periodicity are of considerable interest in a wide range of fields, with various possible applications ranging from biomedical to nanoelectronic devices. Block-copolymer (BC)-based lithography is a powerful tool for the fabrication of uniform, densely spaced nanometer-scale features over large areas. Following this bottom-up approach, nanoporous polymeric films can be deposited on any type of substrate. The nanoporous periodic template can be transferred to the underlying substrate by dry anisotropic etching. Nevertheless the physical sizes of the polymeric mask represent an important limitation in the implementation of suitable lithographic protocols based on BC technology, since the diameter and the center-to-center distance of the pores cannot be varied independently in this class of materials. This problem could be overcome by combining block copolymer technology with atomic layer deposition (ALD): by means of BC-based lithography a nanoporous SiO2 template, with well-reproducible characteristic dimensions, can be fabricated and subsequently used as a backbone for the growth of perfectly conformal thin oxide films by ALD. In this work polystyrene-b-poly(methylmethacrylate) (PS-b-PMMA) BC and reactive ion etching are used to fabricate hexagonally packed 23 nm wide nanopores in a 50 nm thick SiO2 matrix. By ALD deposition of Al2O3 thin films onto the nanoporous SiO2 templates, nanostructured Al2O3 surfaces are obtained. By properly adjusting the thickness of the Al2O3 film the dimension of the pores in the oxide films is progressively reduced, with nanometer precision, from the original size down to complete filling of the pores, thus providing a simple and fast strategy for the fabrication of nanoporous Al2O3 surfaces with well-controllable feature size.     

Ordered arrays of <100>-oriented silicon nanorods by CMOS-compatible block copolymer lithography

Dense, ordered arrays of <100>-oriented Si nanorods with uniform aspect ratios up to 5:1 and a uniform diameter of 15 nm were fabricated by block copolymer lithography based on the inverse of the traditional cylindrical hole strategy and reactive ion etching. The reported approach combines control over diameter, orientation, and position of the nanorods and compatibility with complementary metal oxide semiconductor (CMOS) technology because no nonvolatile metals generating deep levels in silicon, such as gold or iron, are involved. The Si nanorod arrays exhibit the same degree of order as the block copolymer templates.     

Fabrication of 3D functionalized microstructure via scanning probe lithography and self-assembly methods

A type of 2-dimensional planar pattern with spatial resolution can be easily produced using scanning probe lithography (SPL). However, it has not been used successfully for fabricating 3-dimensional (3D) structures due to the low aspect ratio of the resulting structure. Herein, we describe a method for fabricating a 3D functionalized structure via a combination of SPL and self-assembly techniques. In this study, a 3D structure was established on a Si surface with a passivated monolayer via SPL. The patterned layer was modified using a omega-functionalized organosilane. Lateral force microscopy (LFM) was applied to discriminate the chemical functionalities and gold nanoparticles were also used to clearly identify the modified layer.     

Micropatterning of Ag and Au nanoparticles by microcontact printing and block copolymer micelles

Micropatterns of gold and silver nanoparticles were successfully obtained by combining microcontact printing and poly(2-vinylpyridine)-block-poly(cyclohexyl metharylate) (P2VP-b-PCHMA) diblock copolymer micelles with metal precursors. The metal ions were incorporated into poly(2-vinylpyridine) blocks and located into the core area of micelles. Then the metal-loaded micellar solutions were used as inks which were spin coated as thin layers onto polydimethylsiloxane stamps and transferred onto the substrates by stamping. Different morphologies of micellar aggregates were formed on the substrates depending on the stamp morphologies, and single layers of nanoparticles in the micropattern were obtained by the reducing process.     

Implementation of atomically defined field ion microscopy tips in scanning probe microscopy

The field ion microscope (FIM) can be used to characterize the atomic configuration of the apices of sharp tips. These tips are well suited for scanning probe microscope (SPM) use since they predetermine the SPM resolution and the electronic structure for spectroscopy. A protocol is proposed for preserving the atomic structure of the tip apex from etching due to gas impurities during the period of transfer from the FIM to the SPM, and estimations are made regarding the time limitations of such an experiment due to contamination with ultra-high vacuum rest gases. While avoiding any current setpoint overshoot to preserve the tip integrity, we present results from approaches of atomically defined tungsten tips to the tunneling regime with Au(111), HOPG (highly oriented pyrolytic graphite) and Si(111) surfaces at room temperature. We conclude from these experiments that adatom mobility and physisorbed gas on the sample surface limit the choice of surfaces for which the tip integrity is preserved in tunneling experiments at room temperature. The atomic structure of FIM tip apices is unchanged only after tunneling to the highly reactive Si(111) surface.     

Crack toughness behavior of binary poly(styrene-butadiene) block copolymer blends

Fracture behavior of binary blends comprising styrene-butadiene block copolymers having star and triblock architectures was studied by instrumented Charpy impact test. The toughness of the ductile blends was characterized by the dynamic crack resistance concept (R curves). While the lamellar thermoplastic star block copolymer shows elastic behavior (small scale yielding and unstable crack growth), adding 20 wt% of a triblock copolymer (thermoplastic elastomer, TPE) leads to a strong increase in crack toughness. The stable crack propagation behavior of these blends was described by the crack resistance curve (R) concept of elastic-plastic fracture mechanics. This concept allows the determination of fracture mechanics parameters as resistance against stable crack initiation and propagation. Two brittle to tough transitions (BTT) are observed in the binary block copolymer blend: BTT1 at 20% TPE and BTT2 at about 60% TPE. The strong increase of toughness at 60 wt% TPE indicates a tough/high-impact transition as a measure for the protection against stable crack initiation.The kinetics of stable crack propagation is discussed with respect to deformation mechanisms and crack-tip blunting behavior. The analysis of fracture surface by SEM revealed three different types of deformation mechanisms depending on the weight fraction of TPE: coalescence of microvoids (similar to semicrystalline polymers), shear flow (typical of many amorphous polymers like polycarbonate) and tearing (similar to elastomers). Our investigations on nanostructured binary block copolymer blends show new possibilities to tailor the toughness of polymer materials associated with complex morphology-toughness correlations. This may lead to new materials concepts for toughened nanostructured polymers, which still maintain excellent transparency.     

Morphological analysis of self-assembled SIS block copolymer matrices containing silver nanoparticles

The intrinsic ability of block copolymers to self-assemble at nanoordered level into different nanoscale structures has been used in this study to obtain nanocomposites. Ordered architectures of silver nanoparticles confined in a poly(styrene-b-isoprene-b-styrene) (SIS) block copolymer matrix have been generated. Both cetyl trimethylammonium chloride (TMAC) and dodecanethiol (DT) were used as surfactants to obtain dispersed nanocomposite films. Morphologies generated in Ag/SIS nanocomposites, detected through atomic force, resulted to be more dependent on the amount of silver nanoparticles than on the other variables chosen in the present study such as amount and type of surfactant and preparation parameters. The experimental observations are consistent with phase diagram predictions obtained for hybrid systems composed of block copolymers and nanoparticles.     

Fabrication of Ni nanostructures on p-Si by scanning probe lithography on Si3N4 films and selective electrodeposition

Ni-Si nano Schottky junctions are fabricated by the combined process of scanning probe lithography and electrodeposition. The Si3N4 film was patterned by probe-induced oxidation and became a mask for selective electrodeposition of Ni on p-Si substrate. The Ni pattern consists of Ni nano dots, whose diameter is less then 60 nm. The composition and ferromagnetism of Ni dots are verified by energy dispersive spectrum and magnetic force microscopy. The schottky barrier of Ni-Si nano contact is 0.52 V determined by the I-V measurement of conducting atomic force microscopy (CAFM). From current mapping images, it shows that chemical impurity at the Ni-Si interfaces can result in the poor conductance of the junctions.     

Organization of nanoparticles on hard substrates using block copolymer films as templates

We present a technique for the organization of pre-synthesized nanoparticles on hard substrates, using block copolymer films as sacrificial templates. A thin block copolymer film is dip-coated on the substrate of interest and the sample is exposed to a solution containing nanoparticles. Spontaneous preferential adsorption of the nanoparticles on one phase of the block copolymer film results in their lateral organization. An oxygen plasma etch is used to remove the polymer film; the nanoparticles end up organized on the substrate. We demonstrate that this is a general approach for the patterning of inorganic nanoparticles on hard substrates, showing the organization of metal and semiconductor nanoparticles having different chemistries at the particle/solvent and solvent/polymer interfaces. The nanoparticle patterns that we present have typical periodicities in the nanometer scale. In some cases, microcontact printing is used to create a double length scale of organization, on the micrometer and on the nanometer level. The characteristic periodicity of the template is studied with respect to the nanoparticle size in order to optimize the organization. Finally, we describe how to extend this technique for the production of continuous gold nanowires on hard substrates. We expect that the flexibility of this approach and the degree of control that can be obtained over nanoparticle organization should make it a powerful tool for nanoscale fabrication.     

Hybrid, elastomeric hydrogels crosslinked by multifunctional block copolymer micelles

Amphiphlic block copolymers consisting of hydrophilic, poly(acrylic acid) randomly decorated with acrylate groups and hydrophobic, rubbery poly(n-butyl acrylate) self-assembled into well-defined micelles with an average diameter of ~21 nm. Radical polymerization of acrylamide in the presence of the crosslinkable micelles gave rise to hybrid, elastomeric hydrogels whose mechancial properties can be readily tuned by varying the BCM concentration.     

Stability of Ag nanoparticles fabricated by electron beam lithography

The stability of silver nanoparticles on indium tin oxide coated glass substrates under atmospheric condition was investigated. These nanoparticles were fabricated using electron beam lithography. Energy dispersive spectroscopy analysis revealed a high concentration of sulfur in the silver nanoparticles exposed to laboratory air for 12 weeks at room temperature. Morphological changes in the silver nanoparticles were also observed for nanoparticles stored under the same conditions. In contrast, silver nanoparticles kept in vacuum did not show chemical or morphological changes after 12 weeks. The present work clearly shows the need to consider ambient exposure when using Ag nanoparticles for sensors.