Lithographically patterned micro-/nanostructures via colloidal lithography

Colloidal lithography is an effective and facile strategy for highly ordered nanostructure arrays that is a simple, inexpensive, and high-throughput process with a broad choice of materials in manufacturing various lithographically patterned nanostructures on substrates. To develop such nanostructured systems, various nanofabrication techniques are employed on two-dimensional (2D) colloidal masks for evaporation, electrochemical deposition, etching, dewetting and mask replication. Ordered nanostructures associated with feature shapes and sizes can be diversified through a choice of methodology and a control of experimental conditions. This review presents an overview of colloidal crystals as a mask and nanostructure arrays (nanopillars, nanoring, nanopores) fabricated by colloidal lithography as well as introducing practical applications using ordered nanostructures.     

Ordered macroporous bimetallic nanostructures: design, characterization, and applications

Ordered porous metal nanomaterials have current and future potential applications, for example, as catalysts, as photonic crystals, as sensors, as porous electrodes, as substrates for surface-enhanced Raman scattering (SERS), in separation technology, and in other emerging nanotechnologies. Methods for creating such materials are commonly characterized as "templating", a technique that involves first the creation of a sacrificial template with a specific porous structure, followed by the filling of these pores with desired metal materials and finally the removal of the starting template, leaving behind a metal replica of the original template. From the viewpoint of practical applications, ordered metal nanostructures with hierarchical porosity, namely, macropores in combination with micropores or mesopores, are of particular interest because macropores allow large guest molecules to access and an efficient mass transport through the porous structures is enabled while the micropores or mesopores enhance the selectivity and the surface area of the metal nanostructures. For this objective, colloidal crystals (or artificial opals) consisting of three-dimensional (3D) long-range ordered arrays of silica or polymer microspheres are ideal starting templates. However, with respect to the colloidal crystal templating strategies for production of ordered porous metal nanostructures, there are two challenging questions for materials scientists: (1) how to uniformly and controllably fill the interstitial space of the colloidal crystal templates and (2) how to generate ordered composite metal nanostructures with hierarchical porosity. This Account reports on recent work in the development and applications of ordered macroporous bimetallic nanostructures in our laboratories. A series of strategies have been explored to address the challenges in colloidal crystal template techniques. By rationally tailoring experimental parameters, we could readily and selectively design different types of ordered bimetallic nanostructures with hierarchical porosity by using a general template technique. The applications of the resulting nanostructures in catalysis and as substrates for SERS are described. Taking the ordered porous Au/Pt nanostructures as examples for applications as catalysts, the experimental results show that both the ordered hollow Au/Pt nanostructure and the ordered macroporous Au/Pt nanostructure exhibit high catalytic ability due to their special structural characteristics, and their catalytic activity is component-dependent. As for SERS applications, primary experimental results show that these ordered macroporous Au/Ag nanostructured films are highly desirable for detection of DNA bases by the SERS technique in terms of a high Raman intensity enhancement, good stability, and reproducibility, suggesting that these nanostructures may find applications in the rapid detection of DNA and DNA fragments.     

Template-free fabrication of silicon micropillar/nanowire composite structure by one-step etching

A template-free fabrication method for silicon nanostructures, such as silicon micropillar (MP)/nanowire (NW) composite structure is presented. Utilizing an improved metal-assisted electroless etching (MAEE) of silicon in KMnO₄/AgNO₃/HF solution and silicon composite nanostructure of the long MPs erected in the short NWs arrays were generated on the silicon substrate. The morphology evolution of the MP/NW composite nanostructure and the role of self-growing K₂SiF₆ particles as the templates during the MAEE process were investigated in detail. Meanwhile, a fabrication mechanism based on the etching of silver nanoparticles (catalyzed) and the masking of K₂SiF₆ particles is proposed, which gives guidance for fabricating different silicon nanostructures, such as NW and MP arrays. This one-step method provides a simple and cost-effective way to fabricate silicon nanostructures.     

Preparation of phenolic resin derived 3-D ordered macroporous carbon

Three-dimensionally ordered long-range macroporous carbon structures were prepared using commercially available phenolic resin by utilizing sacrificial colloidal silica crystalline arrays as templates that were subsequently removed by HF etching after pyrolysis in an argon atmosphere. SEM, TEM, and BET were employed to characterize the morphology and the surface area of the porous carbon structures. The pore size (150–1000 nm) and BET surface area, which reflect pore volume (298.6 m²/g (1.32 cm³/g) ∼ 93.7 m²/g (0.12 cm³/g)), of the macroporous carbon structures produced were approximately proportional to the size (150–1000 nm) of the sacrificial silica sphere templates used (annealing temp. 550°C). The achieved 550 nm porous carbon structures were examined to function as potential catalyst carriers and were successfully impregnated with Ag or Pt-Ru on their inner walls after borohydride reduction at room temperature. In addition, porous carbon patterns were fabricated using the ‘micromolding in capillary’ technique, which has potential applications in the microreaction technology.     

Fabrication of the periodic nanopillar arrays by heat-induced deformation of 2D polymer colloidal monolayer

A strategy based on heat-deformable monolayer polymer (polystyrene) colloidal template and precursor solution-dipping is presented to fabricate large-scale nanopillar arrays. In the method, the appropriate heating time of the polymer colloidal templates is a key factor. Fe₂O₃ and silica hexagonal periodic triangular prism nanopillar arrays with an aspect ratio of about 1.5:1 were successfully fabricated. This route is also applicable for synthesis of other material nanopillar arrays and opens a new way to create patterned 1D nanostructures for applications in sensor arrays, piezoelectric antenna arrays, optoelectronic devices, superhydrophobic and self-cleaning surfaces.     

One-dimensional hybrid nanostructures: synthesis via layer-by-layer assembly and applications

Assembly techniques are being intensely sought for preparing nanocomposites with tunable compositions and structures. Compared to other assembly techniques, the layer-by-layer (LBL) technique, which is based on the electrostatic attraction between oppositely charged species, provides a simple, versatile and powerful method to synthesize various types of one-dimensional (1D) hybrid nanostructures. In this review, we begin with the developments in the LBL synthesis of nanocomposites, with a focus on our recent results for synthesizing 1D hybrid nanostructures via LBL assembly. Compared to previous LBL processes, we conducted the in situ reaction on the surface of 1D nanostructures via electrostatic attraction between oppositely charged 1D nanostructures and ions in the solution in an attempt to produce 1D hybrid nanostructures. Moreover, these core-shell nanostructures can be transformed into nanotubes by the removal of the templates. The as-synthesized 1D hybrid nanostructures and nanotubes with tunable composition exhibited enhanced performance for various applications such as gas sensors, lithium-ion batteries and cellular imaging.     

Surface-Enhanced Raman Scattering from Dye Molecules in Silicon Nanowire Structures Decorated by Gold Nanoparticles

Silicon nanowires (SiNWs) prepared by metal-assisted chemical etching of crystalline silicon wafers followed by deposition of plasmonic gold (Au) nanoparticles (NPs) were explored as templates for surface-enhanced Raman scattering (SERS) from probe molecules of Methylene blue and Rhodamine B. The filling factor by pores (porosity) of SiNW arrays was found to control the SERS efficiency, and the maximal enhancement was observed for the samples with porosity of 55%, which corresponded to dense arrays of SiNWs. The obtained results are discussed in terms of the electromagnetic enhancement of SERS related to the localized surface plasmon resonances in Au-NPs on SiNW’s surfaces accompanied with light scattering in the SiNW arrays. The observed SERS effect combined with the high stability of Au-NPs, scalability, and relatively simple preparation method are promising for the application of SiNW:Au-NP hybrid nanostructures as templates in molecular sensorics.     

Large area nanopatterning of alkylphosphonate self-assembled monolayers on titanium oxide surfaces by interferometric lithography

We demonstrate that interferometric lithography offers a fast, simple route to nanostructured self-assembled monolayers of alkylphosphonates on the native oxide of titanium. Exposure at 244 nm using a Lloyd's mirror interferometer caused the spatially periodic photocatalytic degradation of the adsorbates, yielding nanopatterns that extended over square centimetre areas. Exposed regions were re-functionalised by a second, contrasting alkylphosphonate, and the resulting patterns were used as templates for the assembly of molecular nanostructures; we demonstrate the fabrication of lines of polymer nanoparticles 46 nm wide. Nanopatterned monolayers were also employed as resists for etching of the metal film. Wires were formed with widths that could be varied between 46 and 126 nm simply by changing the exposure time. Square arrays of Ti dots as small as 35 nm (λ/7) were fabricated using two orthogonal exposures followed by wet etching.     

Plasmonic enhancements of photoluminescence in hybrid Si nanostructures with Au fabricated by fully top-down lithography

The authors study plasmonic enhancements of photoluminescence (PL) in Si nanodisk (ND) arrays hybridized with nanostructures such as nanoplates of Au, where these hybrid nanostructures are fabricated by fully top-down lithography: neutral-beam etching using bio-nano-templates and high-resolution electron-beam lithography. The separation distance between the Si ND and Au nanostructure surfaces is precisely controlled by inserting a thin SiO₂ layer with a thickness of 3 nm. We observe that PL intensities in the Si NDs are enhanced by factors up to 5 depending on the wavelength by integrating with the Au nanoplates. These enhancements also depend on the size and shape of the Au nanoplates.     

Fabrication of size-controllable Fe2O3 nanoring array via colloidal lithography

Tailed-Fe(2)O(3) ring arrays are fabricated by solution-dipping on a colloidal monolayer template. The influence of synthesis parameters on the quality of nanostructures has been investigated. The ring size can be controlled by changing the precursor concentration and varying the annealing time of the polystyrene sphere colloidal monolayer. In addition, the edge of the rings is sensitive to the surface tension of precursor solution, and high quality ordered ring arrays can be obtained by tuning the surface tension. This strategy allows the fabrication of specific metal oxides ring arrays with high quality and uniform morphology.     

Magnetic assembly route to colloidal responsive photonic nanostructures

Responsive photonic structures can respond to external stimuli by transmitting optical signals. Because of their important technological applications such as color signage and displays, biological and chemical sensors, security devices, ink and paints, military camouflage, and various optoelectronic devices, researchers have focused on developing these functional materials. Conventionally, self-assembled colloidal crystals containing periodically arranged dielectric materials have served as the predominant starting frameworks. Stimulus-responsive materials are incorporated into the periodic structures either as the initial building blocks or as the surrounding matrix so that the photonic properties can be tuned. Although researchers have proposed various versions of responsive photonic structures, the low efficiency of fabrication through self-assembly, narrow tunability, slow responses to the external stimuli, incomplete reversibility, and the challenge of integrating them into existing photonic devices have limited their practical application. In this Account, we describe how magnetic fields can guide the assembly of superparamagnetic colloidal building blocks into periodically arranged particle arrays and how the photonic properties of the resulting structures can be reversibly tuned by manipulating the external magnetic fields. The application of the external magnetic field instantly induces a strong magnetic dipole-dipole interparticle attraction within the dispersion of superparamagnetic particles, which creates one-dimensional chains that each contains a string of particles. The balance between the magnetic attraction and the interparticle repulsions, such as the electrostatic force, defines the interparticle separation. By employing uniform superparamagnetic particles of appropriate sizes and surface charges, we can create one-dimensional periodicity, which leads to strong optical diffraction. Acting remotely over a large distance, magnetic forces drove the rapid formation of colloidal photonic arrays with a wide range of interparticle spacing. They also allowed instant tuning of the photonic properties because they manipulated the interparticle force balance, which changed the orientation of the colloidal assemblies or their periodicity. This magnetically responsive photonic system provides a new platform for chromatic applications: these colloidal particles assemble instantly into ordered arrays with widely, rapidly, and reversibly tunable structural colors, which can be easily and rapidly fixed in a curable polymer matrix. Based on these unique features, we demonstrated many applications of this system, such as structural color printing, the fabrication of anticounterfeiting devices, switchable signage, and field-responsive color displays. We also extended this idea to rapidly organize uniform nonmagnetic building blocks into photonic structures. Using a stable ferrofluid of highly charged magnetic nanoparticles, we created virtual magnetic moments inside the nonmagnetic particles. This "magnetic hole" strategy greatly broadens the scope of the magnetic assembly approach to the fabrication of tunable photonic structures from various dielectric materials.     

Fabrication of versatile nanoporous templates with high aspect ratios by incorporation of Si-containing block copolymer into the lithographic bilayer system

We report a new approach to fabricate versatile nanoporous templates with high aspect ratios by incorporating silicon-containing block copolymers into the lithographic bilayer system. This approach used a top thin film of self-assembled asymmetric polystyrene-block-poly(4-(tert-butyldimethylsilyl)oxystyrene) (PS-b-PSSi) as a hard etch mask and an underlying thick film of a negative-tone photoresist (SU-8) for pattern transfer. The assembly of PS-b-PSSi was well-controlled by solvent annealing on the SU-8 and deep nanopores were formed in the underlying layer by oxygen reactive ion etching due to high etch contrast. As a result, highly dense and uniform nanoporous templates with high aspect ratios were obtained over a large area. These templates have versatilities to easily control the sizes of nanopores and to make on the diverse functional substrates. Moreover, the dry-etch process during removal of nanotemplates prevented collapse and aggregation of nanostructures. As a demonstration, we fabricated vertically ordered freestanding gold nanorod arrays by using these templates.     

Synthesis and field emission properties of different ZnO nanostructure arrays

In this article, zinc oxide (ZnO) nanostructures of different shapes were fabricated on silicon substrate. Well-aligned and long ZnO nanowire (NW) arrays, as well as leaf-like ZnO nanostructures (which consist of modulated and single-phase structures), were fabricated by a chemical vapor deposition (CVD) method without the assistance of a catalyst. On the other hand, needle-like ZnO NW arrays were first fabricated with the CVD process followed by chemical etching of the NW arrays. The use of chemical etching provides a low-cost and convenient method of obtaining the needle-like arrays. In addition, the field emission properties of the different ZnO NW arrays were also investigated where some differences in the turn-on field and the field-enhancement factors were observed for the ZnO nanostructures of different lengths and shapes. It was experimentally observed that the leaf-like ZnO nanostructure is most suitable for field emission due to its lowest turn-on and threshold field as well as its high field-enhancement factor among the different synthesized nanostructures.     

A versatile synthesis method of dendrites-free segmented nanowires with a precise size control

ABSTRACT: We report an innovative strategy to obtain cylindrical nanowires combining well established and low-cost bottom-up methods such as template-assisted nanowires synthesis and electrodeposition process. This approach allows the growth of single-layer or multi-segmented nanowires with precise control over their length (from few nanometers to several micrometers). The employed techniques give rise to branched pores at the bottom of the templates and consequently dendrites at the end of the nanowires. With our method, these undesired features are easily removed from the nanowires by a selective chemical etching. This is crucial for magnetic characterizations where such non-homogeneous branches may introduce undesired features into the final magnetic response. The obtained structures show extremely narrow distributions in diameter and length, improved robustness and high-yield, making this versatile approach strongly compatible with large scale production at an industrial level. Finally, we show the possibility to tune accurately the size of the nanostructures and consequently provide an easy control over the magnetic properties of these nanostructures.     

A mini review: Functional nanostructuring with perfectly-ordered anodic aluminum oxide template for energy conversion and storage

Nanostructures have drawn great attentions for functional device applications. Among the various techniques developed for fabricating arrayed nanostructures of functional materials, nanostructuring technique with porous anodic aluminum oxide (AAO) membrane as templates becomes more attractive owing to the superior geometrical characteristics and low-cost preparation process. In this mini review, we summarize our recent progress about functional nanostructuring based on perfectly-ordered AAO membrane to prepare perfectly-ordered nanostructure arrays of functional materials toward constructing high-performance energy conversion and storage devices. By employing the perfectly-ordered AAO membrane as templates, arrayed nanostructures in the form of nanodot, nanorod, nanotube and nanopore have been synthesized over a large area. These as-obtained nanostructure arrays have large specific surface area, high regularity, large-scale implementation, and tunable nanoscale features. All these advanced features enable them to be of great advantage for the performance improvement of energy conversion and storage devices, including photoelectrochemical water splitting cells, supercapacitors, and batteries, etc.

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Superparamagnetic iron oxide nanoparticle attachment on array of micro test tubes and microbeakers formed on p-type silicon substrate for biosensor applications

A uniformly distributed array of micro test tubes and microbeakers is formed on a p-type silicon substrate with tunable cross-section and distance of separation by anodic etching of the silicon wafer in N, N-dimethylformamide and hydrofluoric acid, which essentially leads to the formation of macroporous silicon templates. A reasonable control over the dimensions of the structures could be achieved by tailoring the formation parameters, primarily the wafer resistivity. For a micro test tube, the cross-section (i.e., the pore size) as well as the distance of separation between two adjacent test tubes (i.e., inter-pore distance) is typically approximately 1 μm, whereas, for a microbeaker the pore size exceeds 1.5 μm and the inter-pore distance could be less than 100 nm. We successfully synthesized superparamagnetic iron oxide nanoparticles (SPIONs), with average particle size approximately 20 nm and attached them on the porous silicon chip surface as well as on the pore walls. Such SPION-coated arrays of micro test tubes and microbeakers are potential candidates for biosensors because of the biocompatibility of both silicon and SPIONs. As acquisition of data via microarray is an essential attribute of high throughput bio-sensing, the proposed nanostructured array may be a promising step in this direction.     

Lithography-free fabrication of silicon nanowire and nanohole arrays by metal-assisted chemical etching

We demonstrated a novel, simple, and low-cost method to fabricate silicon nanowire (SiNW) arrays and silicon nanohole (SiNH) arrays based on thin silver (Ag) film dewetting process combined with metal-assisted chemical etching. Ag mesh with holes and semispherical Ag nanoparticles can be prepared by simple thermal annealing of Ag thin film on a silicon substrate. Both the diameter and the distribution of mesh holes as well as the nanoparticles can be manipulated by the film thickness and the annealing temperature. The silicon underneath Ag coverage was etched off with the catalysis of metal in an aqueous solution containing HF and an oxidant, which form silicon nanostructures (either SiNW or SiNH arrays). The morphologies of the corresponding etched SiNW and SiNH arrays matched well with that of Ag holes and nanoparticles. This novel method allows lithography-free fabrication of the SiNW and SiNH arrays with control of the size and distribution.     

Programmable nanoengineering templates for fabrication of three-dimensional nanophotonic structures

Porous anodic alumina membranes (AAMs) have attracted great amount of attention due to their potential application as templates for nanoengineering. Template-guided fabrication and assembly of nanomaterials based on AAMs are cost-effective and scalable methods to program and engineer the shape and morphology of nanostructures and nanomaterials. In this work, perfectly ordered AAMs with the record large pitch up to 3 μm have been fabricated by properly controlling the anodization conditions and utilization of nanoimprint technique. Due to the capability of programmable structural design and fabrication, a variety of nanostructures, including nanopillar arrays, nanotower arrays, and nanocone arrays, have been successfully fabricated using nanoengineered AAM templates. Particularly, amorphous Si nanocones have been fabricated as three-dimensional nanophotonic structures with the characterization of their intriguing optical anti-reflection property. These results directly indicate the potential application of the reported approach for photonics and optoelectronics.     

Densely aligned rutile TiO(2) nanorod arrays with high surface area for efficient dye-sensitized solar cells

One-dimensional (1-D) TiO(2) nanorod arrays (NRAs) with large inner surface area are desired in dye-sensitized solar cells (DSSCs). So far, good performance of DSSCs based on 1-D rutile TiO(2) NRAs remains a challenge mainly owing to their low dye-loading ability resulting from the insufficient specific surface area of 1-D TiO(2) nanostructures. In this paper, densely aligned TiO(2) NRAs with tunable thickness were grown directly on transparent conductive fluorine-doped tin oxide (FTO) substrates by hydrothermal method, followed by a facile chemical etching route to further increase the specific surface area of the TiO(2) NRAs. The etching treatment leads to the split of TiO(2) nanorods into secondary nanorods with a reduced diameter, which markedly enlarges the inner surface area of the TiO(2) NRAs. The formation of 1-D rutile TiO(2) nanotube arrays (NTAs) is observed as well in the etched TiO(2) films. Finally, a DSSC efficiency of 5.94% was achieved by utilizing an etched TiO(2) NRA as the photoanode, which is so far the best DSSC efficiency that has been reported for the 1-D rutile TiO(2) NRA films.     

Study of the Formation of Nano-Networks in Colloidal Particles

The authors studied the formation of a wafer-scale network of connected colloidal beads by reactive ion etching. The dimensions of the connections have been studied as a function of etching time for colloidal beads of different sizes, and could be well controlled. The authors have found that the nano-network forms and disappears for the same time of etching independent of the diameter of the polystyrene beads. With recent interest of connected colloidal networks in various optical sensing applications, such as photonic crystals, as surface-enhanced Raman scattering substrates, the studies have potential uses in the development of wafer-scale nanophotonic sensors.