Self-assembled Arrays Research Articles

Bistability of magnetic states in Fe-Pd nanocap arrays

Magnetic bistability between vortex and single domain states in nanostructures are of great interest from both fundamental and technological perspectives. In soft magnetic nanostructures, the transition from a uniform collinear magnetic state to a vortex state (or vice versa) induced by a magnetic field involves an energy barrier. If the thermal energy is large enough for overcoming this energy barrier, magnetic bistability with a hysteresis-free switching occurs between the two magnetic states. In this work, we tune this energy barrier by tailoring the composition of FePd alloys, which were deposited onto self-assembled particle arrays forming magnetic vortex structures on top of the particles. The bifurcation temperature, where a hysteresis-free transition occurs, was extracted from the temperature dependence of the annihilation and nucleation field which increases almost linearly with Fe content of the magnetic alloy. This study provides insights into the magnetization reversal process associated with magnetic bistability, which allows adjusting the bifurcation temperature range by the material properties of the nanosystem.

Surface Lattice Resonances in Self-Assembled Arrays of Monodisperse Ag Cuboctahedra.

Plasmonic metal nanoparticles arranged in periodic arrays can generate surface lattice plasmon resonances (SLRs) with high Q-factors. These collective resonances are interesting because the associated electromagnetic field is delocalized throughout the plane of the array, enabling applications such as biosensing and nanolasing. In most cases such periodic nanostructures are created via top-down nanofabrication processes. Here we describe a capillary-force-assisted particle assembly method (CAPA) to assemble monodisperse single-crystal colloidal Ag cuboctahedra into nearly defect-free >1 cm2 hexagonal lattices. These arrays are large enough to be measured with conventional ultraviolet-visible spectroscopy, which revealed an extinction peak with a Q-factor of 30 at orthogonal illumination and up to 80 at oblique illumination angles. We explain how the experimental extinction changes with different light polarizations and angles of incidence, and compare the evolution of the peaks with computational models based on the coupled dipole approximation and the finite element method. These arrays can support high Q-factors even when exposed to air, because of the high aspect ratio of the single-crystal nanoparticles. The observation of SLRs in a self-assembled system demonstrates that a high level of long-range positional control can be achieved at the single-particle level.

Oriented Gold Nanorod Arrays: Self-Assembly and Optoelectronic Applications.

Self-assembly of anisotropic plasmonic nanomaterials into ordered superstructures has become popular in nanoscience because of their unique anisotropic optical and electronic properties. Gold nanorods (GNRs) are a well-defined functional building block for fabrication of these superstructures. They possess important anisotropic plasmonic characteristics that result from strong local electric field and are responsive to visible and near-IR light. There are recent examples of assembling the GNRs into ordered arrays or superstructures through processes such as solvent evaporation and interfacial assembly. In this Minireview, recent progress in the development of the self-assembled GNR arrays is described, with focus on the formation of oriented GNR arrays on substrates. Key driving forces are discussed, and different strategies and self-assembly processes of forming oriented GNR arrays are presented. The applications of the oriented GNR arrays in optoelectronic devices are also overviewed, especially surface enhanced Raman scattering (SERS).

Growth temperature dependence of cubic GaN step structures and cubic InN dot arrays grown on MgO (001) vicinal substrates

In this paper, we report on the detailed structural features of step-bunched surface formed on cubic (c-) GaN and self-assembled c-InN dot arrays grown on the c-GaN surface, particularly focusing on the growth temperature dependence. Samples were fabricated on MgO (001) vicinal substrates with off-cut angles of 2.0° and 3.5° toward [110] by RF-MBE. Multisteps and terraces with a certain periodicity in the vicinal direction were observed on c-GaN layers. The average terrace width narrowed with lowering the growth temperature and increasing the substrate off-cut angle. The formation of c-InN dots proceeded in the Stranski–Krastanov growth mode with critical thickness of 0.54–0.66 nm. The c-InN dot exhibited a variety of structural features depending on the growth conditions. Positional dot alignment along the multistep edges of the underlayer was observed under some conditions. The degree of alignment was found to be affected by the terrace width on the c-GaN underlayer.

Nanopatterns with a Square Symmetry from an Orthogonal Lamellar Assembly of Block Copolymers.

A nanosquare array is an indispensable element for the integrated circuit design of electronic devices. Block copolymer (BCP) lithography, a promising bottom-up approach for sub-10 nm patterning, has revealed a generic difficulty in the production of square symmetry because of the thermodynamically favored hexagonal packing of self-assembled sphere or cylinder arrays in thin-film geometry. Here, we demonstrate a simple route to square arrays via the orthogonal self-assembly of two lamellar layers on topographically patterned substrates. While bottom lamellar layers within a topographic trench are aligned parallel to the sidewalls, top layers above the trench are perpendicularly oriented to relieve the interfacial energy between grain boundaries. The size and period of the square symmetry are readily controllable with the molecular weight of BCPs. Moreover, such an orthogonal self-assembly can be applied to the formation of complex nanopatterns for advanced applications, including metal nanodot square arrays.

Self-Assembling 2D Arrays with de Novo Protein Building Blocks.

Modular self-assembly of biomolecules in two dimensions (2D) is straightforward with DNA but has been difficult to realize with proteins, due to the lack of modular specificity similar to Watson-Crick base pairing. Here we describe a general approach to design 2D arrays using de novo designed pseudosymmetric protein building blocks. A homodimeric helical bundle was reconnected into a monomeric building block, and the surface was redesigned in Rosetta to enable self-assembly into a 2D array in the C12 layer symmetry group. Two out of ten designed arrays assembled to micrometer scale under negative stain electron microscopy, and displayed the designed lattice geometry with assembly size up to 100 nm under atomic force microscopy. The design of 2D arrays with pseudosymmetric building blocks is an important step toward the design of programmable protein self-assembly via pseudosymmetric patterning of orthogonal binding interfaces.

Dynamic Culture and Selective Extraction of Target Microbial Cells in Self-Assembled Particle Membrane-Integrated Microfluidic Bioreactor Array.

Various microfluidic devices have overcome many disadvantages common to conventional bioreactor systems by enabling active manipulation of cell-culture conditions, monitoring of cellular responses in high-throughput mode, and extraction of target cells in a relatively rapid and low-cost manner. However, existing microfluidic devices still have limitations, including the complexity of their operation and a lack of availability of dynamic control of the chemical environment. Here, we present a novel microfluidic bioreactor array device capable of not only the stable and dynamic programing of cell-culture environments but also the selective extraction of target cells. This device comprises 64 microchambers in a 16 × 4 array format, and each microchamber is integrated with a robust and nanoporous membrane on one side and an H-shaped entrance on the other. The membrane made of self-assembled particles allowed continuous and sequential delivery of various nutrients containing gene inducers to compartmentalized microbial cells, thereby enabling dynamic cell culturing. Additionally, the H-shaped entrance was used for local and selective blocking of the microchamber by employing UV-curable material, thereby enabling the retrieval of target cells from the device while sequestering nontarget cells in the microchambers. Our results demonstrated that the targeted rare cells could be isolated and separated from a mixture of cells by repeating the extraction procedure. Therefore, we anticipate that this microfluidic bioreactor array device will be widely used for not only screening/extraction but also off-chip postanalyses of various microorganisms.

Patterning Nanoparticles with DNA Molds.

We report a nanopatterning strategy in which self-assembled DNA nanostructures serve as structural templates. In previous work, ordering of NPs primarily relied on specific recognition, e.g., DNA-DNA hybridization. Only a few cases have been reported on nonspecific adsorption. Unfortunately, these studies were limited by the integrity and homogeneity of templates and the variety of patterned nanoparticles (NPs). Herein, we have developed a general method to pattern various NPs. The NPs adsorb onto substrate via NP-substrate direct interactions and the substrates are patterned into large arrays (>4 × 4 μm) of tiny, accessible cavities by self-assembled DNA arrays. As a demonstration, DNA templates include tetragonal and hexagonal arrays and the NPs include individual DNA nanomotifs, gold nanoparticles (AuNPs), and proteins. All nanostructures have been confirmed by atomic force microscopy and corresponding fast Fourier transform (FFT) analysis.

Enumerating Circulating Tumor Cells with a Self-Assembled Cell Array (SACA) Chip: A Feasibility Study in Patients with Colorectal Cancer.

Colorectal cancer (CRC) is the second most common cause of cancer-related death worldwide. Detecting and enumerating circulating tumor cells (CTCs) in patients with colorectal cancer emerged as an important prognostic tool which provides a direct estimate of metastatic potential. Improving the turnaround time and decreasing sample volume is critical for incorporating this liquid biopsy tool into routine practice. The objective of the current study was to validate the clinical feasibility of a self-assembled cell array (SACA) chip, a CTC counting platform with less than 4 h turnaround time, in patients with newly diagnosed colorectal cancers. In total, 179 patients with newly diagnosed colorectal cancers from a single institute were enrolled. Epithelial cell adhesion molecule positive (EpCAM(+)), cluster of differentiation 45 negative (CD45(−)) cells were isolated and enumerated from 2 mL of peripheral vein blood (PB) and inferior mesenteric vein blood (IMV) samples obtained during surgery. We found that the CTC count in PB but not IMV correlates with disease stages. Neoadjuvant chemotherapy did not lead to decreased CTC count in both types of blood samples. With cutoffs of four CTCs per 2 mL of blood, and serum carcinoembryonic antigen (CEA) level of 5 ng/mL, patients with non-metastatic disease were more likely to experience recurrence if they had high PB CTC count and high serum CEA concentration (odds ratio, 8.9). Our study demonstrates the feasibility of enumerating CTCs with a SACA chip in patients with colorectal cancer.

Self-assembled colloidal arrays for structural color.

Structural color materials that are colloidally assembled as inspired by nature are attracting increased interest in a wide range of research fields. The assembly of colloidal particles provides a facile and cost-effective strategy for fabricating three-dimensional structural color materials. In this review, the generation mechanisms of structural colors from colloidally assembled photonic crystalline structures (PCSs) and photonic amorphous structures (PASs) are first presented, followed by the state-of-the-art and detailed technologies for their fabrication. The variable optical properties of PASs and PCSs are then discussed, focusing on their spatial long- and short-order structures and surface topography, followed by a detailed description of the modulation of structural color by refractive index and lattice distance. Finally, the current applications of structural color materials colloidally assembled in various fields including biomaterials, microfluidic chips, sensors, displays, and anticounterfeiting are reviewed, together with future applications and tasks to be accomplished.

Supramolecular structures of terbium(iii) porphyrin double-decker complexes on a single-walled carbon nanotube surface.

This work mainly reports the observation of novel supramolecular structures of TbIII-5,15-bisdodecylporphyrin (BDP, C12P) double-decker complexes on the surfaces of single-walled carbon nanotubes (SWNTs) performed by scanning tunneling microscopy under an ultra-high vacuum and low temperature, atomic force microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy, and ultraviolet-visible spectroscopy. The molecules formed a well-ordered self-assembled helix-shaped array with regular periodicity on the tube surface. Additionally, some magnetic properties of the BDP-molecule as well as the resulting BDP-SWNT composites were investigated by superconducting quantum interference measurements. The molecule exhibits single-molecule magnetic (SMM) properties and the composite's magnetization increases almost linearly with decreasing temperature which is possibly due to the coupling between porphyrin molecules and SWNTs. Consequently, this may enable the development of more advanced spintronic devices based on porphyrin-nanocarbon composites.

Структурные и морфологичеcкие свойства гибридных гетероструктур на основе GaN, выращенного на "податливой" подложке por-Si(111)

AbstractThe possibility of synthesizing integrated GaN/por-Si heterostructures by plasma-assisted molecular beam epitaxy without an A1N/Si buffer layer is demonstrated. The beneficial effect of the high-temperature nitridation of a silicon substrate before GaN growth on the crystal quality of the GaN/Si layers is shown. It is established that, to obtain two-dimensional GaN layers on Si(111), it is reasonable to use compliant por-Si substrates and low-temperature GaN seed layers with a 3D morphology synthesized by plasma-assisted molecular beam epitaxy at relatively low substrate temperatures under stoichiometric conditions and upon enrichment with nitrogen. In this case, a self-assembled array of GaN seed nanocolumns with a fairly uniform diameter distribution forms on the por-Si substrate surface. The basic GaN layers, in turn, should be grown at a high temperature under stoichiometric conditions upon enrichment with gallium, upon which the coalescence of nucleated GaN nanocolumns and growth of a continuous two-dimensional GaN layer are observed. The use of compliant Si substrates is a relevant approach for forming GaN-based semiconductor device heterostructures by plasma-assisted molecular beam epitaxy.

Tailoring the interparticle distance in Langmuir nanoparticle films.

The ability to control the interparticle distance in self-assembled arrays of nanoparticles plays an important role in a large number of applications, which require tunable electronic and photonic properties. Importantly, practical applications in real devices rely on arrays satisfying more stringent requirements of lateral homogeneity controlled over a large scale. Herein, the interparticle distance in ordered nanoparticle assemblies was controlled by varying the nanoparticle effective size via the molecular chemical nature and chain length of the ligand. Iron oxide nanoparticles (IONPs) were functionalized by three types of ligands, namely (i) a mixture of oleic acid/oleylamine (OA/OAm), (ii) poly(n-butyl acrylate) (PBA) and (iii) polystyrene (PS), while two different molar masses of PBA and PS were used. The polymeric ligands with narrow dispersity and bearing phosphonic chain-end groups were prepared by atom transfer radical polymerization. Functionalization of the IONPs with polymeric ligands was achieved using a ligand exchange method. Both the hydrodynamic diameter and size distribution of the nanoparticles in colloidal solution were determined by dynamic light scattering (DLS). The mean interparticle distances in Langmuir-Schaefer monolayers prepared on solid substrates were assessed by means of the pair correlation function calculated from the atomic force microscopy (AFM) images. Furthermore, the lateral ordering, homogeneity, and interparticle distances averaged over a mesoscopic scale of the ordered monolayers were studied by the grazing-incidence small-angle X-ray scattering (GISAXS) technique. We demonstrate that the (nanoparticle) centre-to-centre distance in the ordered assemblies constituted by the IONPs with the core diameter of about 6 nm can be varied from 7.6 to about 12 nm with the resulting interparticle gap change by a factor of about 4.

Shape Transformation Photolithography: Self-Assembled Arrays of Suspended MEMS Structures from Patterned Polymer Membranes.

Suspended micromechanical structures are typically formed by dissolving underlying spacer material. However, capillary force-induced collapse during solvent removal can damage soft structures. If instead capillary forces are directed in the plane, they can drive liquid polymeric bridges to directly transform into suspended fibers. The various capillary force-directed methods for fabricating arrays of suspended fibers have suffered from either low manufacturing rates or an inability to produce arbitrary patterns. Shape transformation photolithography (STP) demonstrated herein is a method of producing arbitrarily patterned arrays of suspended fibers that are potentially capable of high fabrication rates. In STP, holes are prepatterned in a polymer nanofilm supported on a micropillar array, and then the film is heated above its glass transition temperature. First, the holes expand by dewetting and then capillary forces drive thinning of the polymer channels defined by the holes. Prepatterning overcomes the energy barrier for hole nucleation and ensures that all fibers form at the same time and with similar diameters. Arrays of fibers and fiber lattice networks are formed from dyed polystyrene films that are patterned with nanosecond laser pulses at 532 nm. The exposure threshold for forming holes is 10.5 mJ/cm2 for single pulses and 3.3 mJ/cm2 per pulse for repetitive pulsing, which is only about 3× larger than the dose available from current 193 nm wafer-stepping projection printers that are used in device manufacture. With the increased absorption of polystyrene at 193 nm and with additional proposed material modifications to the thin film, it may even be possible to employ STP in production wafer steppers at economically feasible manufacturing rates of over 50 wafers/h.

Triangular DNA Origami Tilings

DNA origami tilings provide methods for creating complex molecular patterns and shapes using flat DNA origami structures as building blocks. Square tiles have been developed to construct micrometer-scale arrays and to generate patterns using stochastic or deterministic strategies. Here we show triangular tiles as a complementary approach for enriching the design space of DNA tilings and for extending the shape of the self-assembled arrays from 2D to 3D. We introduce a computational approach for maximizing binding specificity in a fully symmetric tile design, with which we construct a 20-tile structure resembling a rhombic triacontahedron. We demonstrate controlled transition between 3D and 2D structures using simple methods including tile concentration, magnesium, and fold symmetry in tile edge design. Using these approaches, we construct 2D arrays with unbounded and designed sizes. The programmability of the edge design and the flexibility of the structure make the triangular DNA origami tile an ideal building block for complex self-assembly and reconfiguration in artificial molecular machines and fabricated nanodevices.

Self-assembled gold micro/nanostructure arrays based on superionic conductor RbAg4I5 films

Herein, we propose a new strategy to fabricate gold (Au) micro/nanostructure arrays by photocatalytic solid-state electrochemical reaction between superionic conductor RbAg4I5 and Au films. The Au and RbAg4I5 films were successively deposited on a clean quartz substrate by vacuum thermal deposition method. A copper microgrid possessing periodic holes 100 μm in diameter was put above the RbAg4I5 film as a mask plate, whereupon irradiation from a 405 nm wavelength laser was used to diffuse gold ions (Au+ ions) into vacant silver sites of RbAg4I5 and transfer Au+ through ion passageways in the RbAg4I5 film. When the laser was turned off, the Au+ ions were easily reduced due to low activity compared to the silver (Ag+) ions. After multiple on/off cycles of the 405 nm laser, the irradiated area of uniform Au film exhibited a periodic structural unit array whose period was the same as that of the mask plate hole array. Atomic force microscope and scanning electron microscope images revealed that a self-assembled needle-like nanostructure array grew perpendicular to the substrate surface inside each circle’s structural unit. The height of the grown nanostructure array increased with laser power density. Raman enhancement of the gold nanostructure array as substrate was detected using Rhodamine 6G (R6G) ethanol solutions as probe molecules. The enhancement effect increased with the height of the grown nanostructure array, and could increase by two orders of magnitude greater than that of unirradiated Au film. This strategy offers a new method for the micro/nanostructure processing of gold and provides microscale-array-mediated surface-enhancement Raman-scattering (SERS) substrates comprising Au nanostructures for application in high-sensitivity spectrum analysis.

Formation of nanotubular structure on low-modulus Ti–7.5Mo alloy surface and its bioactivity evaluation

This study investigates the use of anodization in NH4F/NaCl electrolyte in the formation of self-assembled nanotube arrays on a Ti–7.5Mo surface. As anodic oxidation potential increased from 5 V to 10 V, the pore size and tube length of the nanotubes gradually increased approximately from 23–27 to 31–44 nm, and 550 to 700 nm. The XRD results indicated that the oxide layers on the surface of the anodized samples were all amorphous structures. After annealing at 450 °C for 3 h, peaks of anatase phase were observed. The results of the XPS analysis showed that the major components on the surfaces of the annealed nanotube arrays were TiO2, MoO2, and MoO3. In vitro testing of the annealed nanotube arrays demonstrated that rapid deposition of apatite spheroids on these nanostructures occurred after only 12 h immersion in simulated body fluids (SBF), a result that was particularly evident in the samples anodized at 10 V. Cell culture experiments showed that the anodized Ti–7.5Mo alloy is biocompatible and can support cell attachment.

Self-assembled porous metal-intermetallic nanocomposites via liquid metal dealloying

A major challenge in the synthesis of high surface area metals via subtractive processes such as dealloying is maintaining the mechanical integrity of the resulting porous materials. This problem is especially apparent in liquid metal dealloying, in which high-temperature selective dissolution in a molten metal bath leads to bicontinuous porosity formation. In liquid metal dealloying of polycrystalline alloys, grain boundary separation leads to the detachment of individual grains. In this work, we show that addition of small amounts of silicon to NbTi or TaTi parent alloys leads to the generation of self-assembled arrays of intermetallic (niobium silicide or tantalum silicide) plates that are structurally merged with the usual bicontinuous porosity seen in dealloying. These silicide plates pass through grain boundaries and hold the niobium or tantalum network intact without strongly affecting the microstructural evolution during dealloying. Our approach yields a mechanically robust porous metal-intermetallic composite, which can be further processed to form tertiary materials via re-impregnation by a new third phase. The materials design strategy introduced here can be generalized to serve as a platform to form dense multiphase nanocomposites.

Fullerenols Revisited: Highly Monodispersed Photoluminescent Nanomaterials as Ideal Building Blocks for Supramolecular Chemistry.

Fullerenols have been known for decades; however, the photoluminescent (PL) properties and applications in supramolecular chemistry of these molecules have not been well addressed. Herein, a strategy has been developed to purify the as-prepared fullerenols, and the photoluminescence and capabilities of these molecules to form supramolecular self-assemblies were systematically studied. It was found that fullerenols show wavelength-dependent emission with an absolute fluorescent quantum yield of approximately 3.5 %. The PL characteristics are reminiscent of carbon dots, especially those obtained by using the top-down method. The studied fullerenols can be used to detect Cu2+ ions with a limit of detection down to 3.50 μm. In addition, the amphiphilicity of the fullerenols can be readily tuned by ionic complexation with cationic surfactants, such as 1-tetradecyl-3-methylimidazoliumbromide (C14 mimB) and tetradecyltrimethylammonium bromide (TTAB). On increasing the concentration of the surfactant, the transition of aggregates was induced from highly ordered vesicles to honeycomb-structured crystals and finally to giant micelles. After the formation of supramolecular self-assemblies, enhancement of photoluminescence was observed, which can be ascribed to the suppression of intramolecular vibrations and motion combined with the loosely packed self-assembly array. This study provides a facile way to generate PL nanoarchitectures, which may find applications in fluorescent sensing, drug delivery, and optoelectronics.

Direct catalyst-free self-assembly of large area of horizontal ferromagnetic ZnO nanowire arrays

Large-area self-assembled horizontal ferromagnetic ZnO nanowire arrays (NWAs) have been successfully prepared by catalyst-free post-annealing treatment on ZnO thin films. XRD, SEM and TEM analysis show that the ZnO nanowires with a hexagonal wurtzite structure are aligned along the 〈112¯0〉 glide directions and the density of wires is an order of magnitude higher than those fabricated using catalyst. Magnetization measurements indicate that the arrays are ferromagnetic at room temperature. It is found that the annealing plays a key role not only in producing nanowire arrays by thermal treatment but also in inducing magnetism by generating vacancies by evaporation. With a high wire density and ferromagnetic ordering, the horizontal NWAs fabricated by the simple annealing method may be useful for fabricating electrical and spintronic devices at nanoscale.