Nanodomain Swelling Block Copolymer Lithography for Morphology Tunable Metal Nanopatterning

Ordered metal nanopatterns are crucial requirements for electronics, magnetics, catalysts, photonics, and so on. Despite considerable progress in the synthetic route to metal nanostructures, highly ordered metal nanopatterning over a large‐area is still challenging. Nanodomain swelling block copolymer lithography is presented as a general route to the systematic morphology tuning of metal nanopatterns from amphiphilic diblock copolymer self‐assembly. Selective swelling of hydrophilic nanocylinder domains in amphiphilic block copolymer films during metal precursor loading and subsequent oxygen based etching generates diverse shapes of metal nanopatterns, including hexagonal nanoring array and hexagonal nanomesh and double line array in addition to common nanodot and nanowire arrays. Solvent annealing condition of block copolymer templates, selective swelling of hydrophilic cylinder nanodomains, block copolymer template thickness, and oxygen based etching methods are the decisive parameters for systematic morphology evolution. The plasmonic properties of ordered Au nanopatterns are characterized and analyzed with finite differential time domain calculation. This approach offers unprecedented opportunity for diverse metal nanopatterns from commonly used diblock copolymer self‐assembly.     

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.     

Graphoepitaxy of cylinder-forming block copolymers for use as templates to pattern magnetic metal dot arrays

We report a method to fabricate high-quality patterned magnetic dot arrays using block copolymer lithography, metal deposition, and a dry lift-off technique. Long-range order of cylindrical domains oriented perpendicular to the substrate and in hexagonal arrays was induced in the block copolymer films by prepatterning the substrate with topographic features and chemically modifying the surface to exhibit neutral wetting behaviour towards the blocks of the copolymer. The uniformity of the domain size and row spacing of block copolymer templates created in this way was improved compared to those reported in previous studies that used graphoepitaxy of sphere-forming block copolymers. The pattern of block copolymer domains was transferred to a pattern of magnetic metal dots, demonstrating the potential of this technology for the fabrication of patterned magnetic recording media.     

Metal‐Assisted Chemical Etching of Silicon: A Review

This article presents an overview of the essential aspects in the fabrication of silicon and some silicon/germanium nanostructures by metal‐assisted chemical etching. First, the basic process and mechanism of metal‐assisted chemical etching is introduced. Then, the various influences of the noble metal, the etchant, temperature, illumination, and intrinsic properties of the silicon substrate (e.g., orientation, doping type, doping level) are presented. The anisotropic and the isotropic etching behaviors of silicon under various conditions are presented. Template‐based metal‐assisted chemical etching methods are introduced, including templates based on nanosphere lithography, anodic aluminum oxide masks, interference lithography, and block‐copolymer masks. The metal‐assisted chemical etching of other semiconductors is also introduced. A brief introduction to the application of Si nanostructures obtained by metal‐assisted chemical etching is given, demonstrating the promising potential applications of metal‐assisted chemical etching. Finally, some open questions in the understanding of metal‐assisted chemical etching are compiled.     

Assembly of aligned linear metallic patterns on silicon

In order to harness the potential of block copolymers to produce nanoscale structures that can be integrated with existing silicon-based technologies, there is a need for compatible chemistries. Block copolymer nanostructures can form a wide variety of two-dimensional patterns, and can be controlled to present long-range order. Here we use the acid-responsive nature of self-assembled monolayers of aligned, horizontal block copolymer cylinders for metal loading with simple aqueous solutions of anionic metal complexes, followed by brief plasma treatment to simultaneously remove the block copolymer and produce metallic nanostructures. Aligned lines of metal with widths on the order of 10 nm and less are efficiently produced by means of this approach on Si(100) interfaces. The method is highly versatile because the chemistry to manipulate nanowire composition, structure and choice of semiconductor is under the control of the user.     

3D Nanofabrication of Fluidic Components by Corner Lithography

A reproducible wafer‐scale method to obtain 3D nanostructures is investigated. This method, called corner lithography, explores the conformal deposition and the subsequent timed isotropic etching of a thin film in a 3D shaped silicon template. The technique leaves a residue of the thin film in sharp concave corners which can be used as structural material or as an inversion mask in subsequent steps. The potential of corner lithography is studied by fabrication of functional 3D microfluidic components, in particular i) novel tips containing nano‐apertures at or near the apex for AFM‐based liquid deposition devices, and ii) a novel particle or cell trapping device using an array of nanowire frames. The use of these arrays of nanowire cages for capturing single primary bovine chondrocytes by a droplet seeding method is successfully demonstrated, and changes in phenotype are observed over time, while retaining them in a well‐defined pattern and 3D microenvironment in a flat array.     

Transparent Plasmonic Nanowire Electrodes via Self‐Organised Ion Beam Nanopatterning

A self‐organised approach for the synthesis of transparent metal nanowire arrays is based on defocused ion beam sputtering. The nanowire arrays, supported on low‐cost dielectric substrates (glass slides), feature a dual functionality: they exhibit anisotropic conductivity, with sheet resistances which are reduced in comparison to those of transparent conductive oxides, and additionally they support localised plasmon resonances. The latter represents an attractive feature in view of plasmon enhanced photon harvesting applications, in which the nanostructured metal electrodes are employed as an alternative to conventional transparent conductive oxides.     

The controlled growth of GaN nanowires

This paper reports a scalable process for the growth of high-quality GaN nanowires and uniform nanowire arrays in which the position and diameter of each nanowire is precisely controlled. The approach is based on conventional metalorganic chemical vapor deposition using regular precursors and requires no additional metal catalyst. The location, orientation, and diameter of each GaN nanowire are controlled using a thin, selective growth mask that is patterned by interferometric lithography. It was found that use of a pulsed MOCVD process allowed the nanowire diameter to remain constant after the nanowires had emerged from the selective growth mask. Vertical GaN nanowire growth rates in excess of 2 mum/h were measured, while remarkably the diameter of each nanowire remained constant over the entire (micrometer) length of the nanowires. The paper reports transmission electron microscopy and photoluminescence data.     

Cover Picture: Templated Fabrication of Nanowire and Nanoring Arrays Based on Interference Lithography and Electrochemical Deposition (Adv. Mater. 19/2006)

On p. 2593, Ji and co‐workers report on a novel fabrication technique for ideally ordered lateral nanowire and nanoring arrays based on interference lithography and electrochemical deposition. This approach allows the fabrication of metallic and semiconductor nanowire or nanoring arrays over wafer‐scale areas and provides flexible control over shape, arrangement, and thickness of the nanowires and nanorings. The cover shows templated electrodeposited elliptical nanoring arrays and a cross‐section of electrodeposited nanowires.     

ZnO nanowire arrays with and without cavity tops

We report a new bubble-assisted growing and etching method for constructing ZnO nanowire (NW) arrays with cavity tops. Firstly, a ZnO NW array structure was formed on a ZnO-seed-layer-patterned Si substrate by combining e-beam lithography and a wet chemical method. Secondly, a new kind of ZnO NW array with cavity tops could be formed by a subsequent bubble-assisted growing and etching. These ZnO NW array structures with different morphologies exhibited different photoluminescence properties, showing their potential applications in lasing cavities, stimulated emitters, nanogenerator, photocatalysis and light-emitting diodes. The bubble-assisted etching method will open a new door for morphology design of ZnO and other semiconductor nanowire arrays at special sites.     

Conducting Polymer Nanowire Arrays for High Performance Supercapacitors

This Review provides a brief summary of the most recent research developments in the fabrication and application of one‐dimensional ordered conducting polymers nanostructure (especially nanowire arrays) and their composites as electrodes for supercapacitors. By controlling the nucleation and growth process of polymerization, aligned conducting polymer nanowire arrays and their composites with nano‐carbon materials can be prepared by employing in situ chemical polymerization or electrochemical polymerization without a template. This kind of nanostructure (such as polypyrrole and polyaniline nanowire arrays) possesses high capacitance, superior rate capability ascribed to large electrochemical surface, and an optimal ion diffusion path in the ordered nanowire structure, which is proved to be an ideal electrode material for high performance supercapacitors. Furthermore, flexible, micro‐scale, threadlike, and multifunctional supercapacitors are introduced based on conducting polyaniline nanowire arrays and their composites. These prototypes of supercapacitors utilize the high flexibility, good processability, and large capacitance of conducting polymers, which efficiently extend the usage of supercapacitors in various situations, and even for a complicated integration system of different electronic devices.     

Arrays of indefinitely long uniform nanowires and nanotubes

Nanowires are arguably the most studied nanomaterial model to make functional devices and arrays. Although there is remarkable maturity in the chemical synthesis of complex nanowire structures, their integration and interfacing to macro systems with high yields and repeatability still require elaborate aligning, positioning and interfacing and post-synthesis techniques. Top-down fabrication methods for nanowire production, such as lithography and electrospinning, have not enjoyed comparable growth. Here we report a new thermal size-reduction process to produce well-ordered, globally oriented, indefinitely long nanowire and nanotube arrays with different materials. The new technique involves iterative co-drawing of hermetically sealed multimaterials in compatible polymer matrices similar to fibre drawing. Globally oriented, endlessly parallel, axially and radially uniform semiconducting and piezoelectric nanowire and nanotube arrays hundreds of metres long, with nanowire diameters less than 15 nm, are obtained. The resulting nanostructures are sealed inside a flexible substrate, facilitating the handling of and electrical contacting to the nanowires. Inexpensive, high-throughput, multimaterial nanowire arrays pave the way for applications including nanowire-based large-area flexible sensor platforms, phase-changememory, nanostructure-enhanced photovoltaics, semiconductor nanophotonics, dielectric metamaterials,linear and nonlinear photonics and nanowire-enabled high-performance composites.     

Toward optimized light utilization in nanowire arrays using scalable nanosphere lithography and selected area growth

Vertically aligned, catalyst-free semiconducting nanowires hold great potential for photovoltaic applications, in which achieving scalable synthesis and optimized optical absorption simultaneously is critical. Here, we report combining nanosphere lithography (NSL) and selected area metal-organic chemical vapor deposition (SA-MOCVD) for the first time for scalable synthesis of vertically aligned gallium arsenide nanowire arrays, and surprisingly, we show that such nanowire arrays with patterning defects due to NSL can be as good as highly ordered nanowire arrays in terms of optical absorption and reflection. Wafer-scale patterning for nanowire synthesis was done using a polystyrene nanosphere template as a mask. Nanowires grown from substrates patterned by NSL show similar structural features to those patterned using electron beam lithography (EBL). Reflection of photons from the NSL-patterned nanowire array was used as a measure of the effect of defects present in the structure. Experimentally, we show that GaAs nanowires as short as 130 nm show reflection of <10% over the visible range of the solar spectrum. Our results indicate that a highly ordered nanowire structure is not necessary: despite the "defects" present in NSL-patterned nanowire arrays, their optical performance is similar to "defect-free" structures patterned by more costly, time-consuming EBL methods. Our scalable approach for synthesis of vertical semiconducting nanowires can have application in high-throughput and low-cost optoelectronic devices, including solar cells.     

Patterning of various silicon structures via polymer lithography and catalytic chemical etching

We demonstrate a facile fabrication of a rich variety of silicon patterns with different length scales by combining polymer lithography and a metal-assisted chemical etching method. Several types of polymer patterns were fabricated on silicon substrates, and silver layers were deposited on the patterned silicon surfaces and used to etch the silicon beneath. Various silicon patterns including topographic lines, concentric rings, and square arrays were created at a micro-?and nanoscale after etching the silicon and subsequent removal of the patterned polymer masks. Alternatively, the arrays of sub-30?nm silicon nanowires were produced by a chemical etching of the silicon wafer which was covered with highly ordered polystyrene-block-polyvinylpyridine (PS-b-PVP) micellar films. In addition, silicon nanohole arrays were also generated by etching with hexagonally packed silver nanoparticles that were prepared using PS-b-PVP block copolymer templates.     

Photopatterning of Cross‐Linkable Epoxide‐Functionalized Block Copolymers and Dual‐Tone Nanostructure Development for Fabrication Across the Nano‐ and Microscales

The self‐assembly of block copolymers in thin films provides an attractive approach to patterning 5–100 nm structures. Cross‐linking and photopatterning of the self‐assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar‐forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self‐assembly and cross‐linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross‐linkable block copolymer materials in thin films and enable simultaneous structure formation across scales—micrometer scale patterns achieved by photolithography and nanostructures via self‐assembly of the block copolymer. Such materials and processes are thus shown to be capable of self‐assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.     

A Simple Top‐Down/Bottom‐Up Approach to Sectored,Ordered Arrays of Nanoscopic Elements Using Block Copolymers

A top‐down/bottom‐up approach is demonstrated by combining electron‐beam (e‐beam) lithography and a solvent annealing process. Micellar arrays of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a high degree of lateral order can be produced on a surface where sectoring is defined by e‐beam patterning. The e‐beam is used to crosslink the block copolymer (BCP) film immediately after spin‐coating when the BCP is disordered or in a highly ordered solvent‐annealed film. Any patterns can be written into the BCP by crosslinking. Upon exposure to a preferential solvent for the minor component block followed by drying, cylindrical nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged. Nickel nanodot arrays can be placed over selected areas on a surface by thermal evaporation and lift‐off process.     

Prereduction of Metal Oxides via Carbon Plasma Treatment for Efficient and Stable Electrocatalytic Hydrogen Evolution

Prereduction of transition metal oxides is a feasible and efficient strategy to enhance their catalytic activity for hydrogen evolution. Unfortunately, the prereduction via the common H₂ annealing method is unstable for nanomaterials during the hydrogen evolution process. Here, using NiMoO₄ nanowire arrays as the example, it is demonstrated that carbon plasma (C‐plasma) treatment can greatly enhance both the catalytic activity and the long‐term stability of transition metal oxides for hydrogen evolution. The C‐plasma treatment has two functions at the same time: it induces partial surface reduction of the NiMoO₄ nanowire to form Ni₄Mo nanoclusters, and simultaneously deposits a thin graphitic carbon shell. As a result, the C‐plasma treated NiMoO₄ can maintain its array morphology, chemical composition, and catalytic activity during long‐term intermittent hydrogen evolution process. This work may pave a new way for simultaneous activation and stabilization of transition metal oxide‐based electrocatalysts.     

Oxide Nanostructures Hyperbranched with Thin and Hollow Metal Shells for High‐Performance Nanostructured Battery Electrodes

High‐performance electrochemical energy storage (EES) devices require the ability to modify and assemble electrode materials with superior reactivity and structural stability. The fabrication of different oxide/metal core‐branch nanoarrays with adjustable components and morphologies (e.g., nanowire and nanoflake) is reported on different conductive substrates. Hollow metal branches (or shells) wrapped around oxide cores are realized by electrodeposition using ZnO nanorods as a sacrificial template. In battery electrode application, the thin hollow metal branches can provide a mechanical protection of the oxide core and a highly conductive path for charges. As a demonstration, arrays of Co₃O₄/Ni core‐branch nanowires are evaluated as the anode for lithium ion batteries. The thin metal branches evidently improve the electrochemical performance with higher specific capacity, rate capability, and capacity retention than the unmodified Co₃O₄ counterparts.     

Fabrication of high-density In(3)Sb(1)Te(2) phase change nanoarray on glass-fabric reinforced flexible substrate

Mushroom-shaped phase change memory (PCM) consisting of a Cr/In(3)Sb(1)Te(2) (IST)/TiN (bottom electrode) nanoarray was fabricated via block copolymer lithography and single-step dry etching with a gas mixture of Ar/Cl(2). The process was performed on a high performance transparent glass-fabric reinforced composite film (GFR Hybrimer) suitable for use as a novel substrate for flexible devices. The use of GFR Hybrimer with low thermal expansion and flat surfaces enabled successful nanoscale patterning of functional phase change materials on flexible substrates. Block copolymer lithography employing asymmetrical block copolymer blends with hexagonal cylindrical self-assembled morphologies resulted in the creation of hexagonal nanoscale PCM cell arrays with an areal density of approximately 176?Gb/in(2).     

Synthesis of metal chalcogenide nanodot arrays using block copolymer-derived nanoreactors

Soluble metal chalcogenide precursors are used to fabricate arrays of metal chalcogenide nanodots by spin-coating. Nanodots are formed after thermal decomposition of the precursors, which are collected in patterned nanowell arrays. These arrays are derived from block copolymer patterns and may consist of the polymer itself or result from etching to transfer the pattern to an inorganic substrate. Etching provides enhanced control over nanowell shape and the morphology of the resulting metal chalcogenide array.