Spontaneous formation of nanoparticle stripe patterns through dewetting

Significant advancement has been made in nanoparticle research, with synthetic techniques extending over a wide range of materials with good control over particle size and shape. A grand challenge is assembling and positioning the nanoparticles in desired locations to construct complex, higher-order functional structures. Controlled positioning of nanoparticles has been achieved in pre-defined templates fabricated by top-down approaches. A self-assembly method, however, is highly desirable because of its simplicity and compatibility with heterogeneous integration processes. Here we report on the spontaneous formation of ordered gold and silver nanoparticle stripe patterns on dewetting a dilute film of polymer-coated nanoparticles floating on a water surface. Well-aligned stripe patterns with tunable orientation, thickness and periodicity at the micrometre scale were obtained by transferring nanoparticles from a floating film onto a substrate in a dip-coating fashion. This facile technique opens up a new avenue for lithography-free patterning of nanoparticle arrays for various applications including, for example, multiplexed surface-enhanced Raman substrates and templated fabrication of higher-order nanostructures.     

Large‐Scale,Long‐Range‐Ordered Patterning of Nanocrystals via Capillary‐Bridge Manipulation

Deterministic assembly of nanoparticles with programmable patterns is a core opportunity for property‐by‐design fabrication and large‐scale integration of functional materials and devices. The wet‐chemical‐synthesized colloidal nanocrystals are compatible with solution assembly techniques, thus possessing advantages of high efficiency, low cost, and large scale. However, conventional solution process suffers from tradeoffs between spatial precision and long‐range order of nanocrystal assembly arising from the uncontrollable dewetting dynamics and fluid flow. Here, a capillary‐bridge manipulation method is demonstrated for directing the dewetting of nanocrystal inks and deterministically patterning long‐range‐ordered superlattice structures. This is achieved by employing micropillars with programmable size, arrangement, and shape, which permits deterministic manipulation of geometry, position, and dewetting dynamics of capillary bridges. Various superlattice structures, including one‐dimensional (1D), circle, square, pentagon, hexagon, pentagram, cross arrays, are fabricated. Compared to the glassy thin films, long‐range‐ordered superlattice arrays exhibit improved ferroelectric polarization. Coassembly of nanocrystal superlattice and organic functional molecule is further demonstrated. Through introducing azobenzene into superlattice arrays, a switchable ferroelectric polarization is realized, which is triggered by order–disorder transition of nanocrystal stacking in reversible isomerization process of azobenzene. This method offers a platform for patterning nanocrystal superlattices and fabricating microdevices with functionalities for multiferroics, electronics, and photonics.     

Synthetically programmable nanoparticle superlattices using a hollow three-dimensional spacer approach

Crystalline nanoparticle arrays and superlattices with well-defined geometries can be synthesized by using appropriate electrostatic, hydrogen-bonding or biological recognition interactions. Although superlattices with many distinct geometries can be produced using these approaches, the library of achievable lattices could be increased by developing a strategy that allows some of the nanoparticles within a binary lattice to be replaced with 'spacer' entities that are constructed to mimic the behaviour of the nanoparticles they replace, even though they do not contain an inorganic core. The inclusion of these spacer entities within a known binary superlattice would effectively delete one set of nanoparticles without affecting the positions of the other set. Here, we show how hollow DNA nanostructures can be used as 'three-dimensional spacers' within nanoparticle superlattices assembled through programmable DNA interactions. We show that this strategy can be used to form superlattices with five distinct symmetries, including one that has never before been observed in any crystalline material.     

Self-assembly versus directed assembly of nanoparticles via pulsed laser induced dewetting of patterned metal films

A nanoscale, synthetic perturbation was all that was required to nudge a natural, self-assembly process toward significantly higher order. Metallic thin film strips were transformed into nanoparticle arrays by nanosecond, liquid-phase dewetting. Arrays formed according to an evolving Rayleigh-Plateau instability, yet nanoparticle diameter and pitch were poorly controlled. However, by patterning a nanoscale sinusoid onto the original strip edge, a precise nanoparticle diameter and pitch emerged superseding the naturally evolving Rayleigh-Plateau instability.     

Self-organized bimetallic Ag-Co nanoparticles with tunable localized surface plasmons showing high environmental stability and sensitivity

We demonstrate a promising synthesis route based on pulsed laser dewetting of bilayer films (Ag and Co) to make bimetallic nanoparticle arrays. By combining experiment and theory we establish a parameter space for the independent control of composition and diameter for the bimetallic nanoparticles. As a result, physical properties, such as the localized surface plasmon resonance (LSPR), that depend on particle size and composition can be readily tuned over a wavelength range one order of magnitude greater than for pure Ag nanoparticles. The LSPR detection sensitivity of the bimetallic nanoparticles with narrow size distribution was found to be high-comparable with pure Ag (～60 nm/RIU). Moreover, they showed significantly higher long-term environmental stability over pure Ag.     

Two-dimensional nanoparticle arrays formed by dewetting of thin gold films deposited on pre-patterned substrates

We demonstrate the formation of accurate 2D gold nanoparticle arrays via solid-state dewetting on a pre-patterned substrate. The annealing-induced dewetting of Au film on both flat and pre-patterned SiO₂ substrates is investigated. The pre-patterned structures affect clearly the formation of nanoparticles, and there is a depth effect of the pre-patterned grooves on the formation of nanoparticles during dewetting. Especially in pre-patterned areas with deep grid grooves (depth 150 nm) there is almost one single particle formed in the flat areas of every unit square, thus resulting in a very periodic 2D structure of gold nanoparticles.     

Cobalt Nanoparticle Arrays made by Templated Solid‐State Dewetting

Self‐assembled cobalt particle arrays are formed by annealing, which cause agglomeration (dewetting) of thin Co films on oxidized silicon substrates that are topographically prepatterned with an array of 200‐nm‐period pits. The Co nanoparticle size and uniformity are related to the initial film thickness, annealing temperature, and template geometry. One particle per 200‐nm‐period pit is formed from a 15‐nm film annealed at 850 °C; on a smooth substrate, the same annealing process forms particles with an average interparticle distance of 200 nm. Laser annealing enables templated dewetting of 5‐nm‐thick films to give one particle per pit. Although the as‐deposited films exhibit a mixture of hexagonal close‐packed and face‐centered cubic (fcc) phases, the ordered cobalt particles are predominantly twinned fcc crystals with weak magnetic anisotropy. Templated dewetting is shown to provide a method for forming arrays of nanoparticles with well‐controlled sizes and positions.     

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.     

Dipole-dipole interactions in nanoparticle superlattices

Nanoparticles often self-assemble into hexagonal-close-packed (hcp) structures although it is predicted to be less stable than face-centered-cubic (fcc) packing in hard-sphere models. In addition to close-packed fcc and hcp superlattices, we observe formation of nonclose-packed simple-hexagonal (sh) superlattices of nearly spherical PbS, PbSe, and gamma-Fe2O3 nanocrystals. This surprisingly rich phase diagram of monodisperse semiconducting nanoparticles is explained by considering the interactions between nonlocal dipoles of individual nanoparticles. By calculating the total electrostatic and dispersive energies, we explain stability of the hcp and sh nanoparticle superlattices, introduce the superlattice phase diagram, and predict antiferroelectric ordering in dipolar nanoparticle superlattices.     

Preparation of monodisperse Ni nanoparticles and their assembly into 3D nanoparticle superlattices

Monodisperse Ni nanoparticles with sizes varying from 4.8 to 11.3 nm are prepared via a one-pot reaction that involves the reduction of nickel(II) acetylacetonate in oleylamine in the presence of trioctylphosphine and 1,2-hexadecanediol. Reaction parameters such as temperature and the concentration of capping agent and metal precursor are critical for the adjustment of particle size. The decrease of crystallinity is observed for the samples with smaller particle sizes, which significantly affects the magnetic properties. Three-dimensional (3D) superlattices that are composed of Ni nanoparticles with different sizes are obtained on different substrates by a facile self-assembly process, and are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and small-angle X-ray diffraction (SAXRD). The Ni nanoparticle superlattices formed on carbon-coated TEM copper grids exhibit a dominant hexagonal close-packed (hcp) symmetry, although local fcc packing is also occasionally observed. The formation of 3D nanoparticle superlattice structures on Si substrates is confirmed from the SAXRD measurements. The method revealed in this study for the preparation of 3D superlattices composed of Ni nanoparticles with tunable sizes offers the potential to explore their interesting collective properties for multiple applications.     

Nanoparticle assemblies in thin films of supramolecular nanocomposites

We demonstrated a versatile approach to obtain layered nanoparticle sheets with in-plane hexagonal order and 3-D ordered arrays of single nanoparticle chains in thin films upon blending nanoparticles with block copolymer (BCP)-based supramolecules. Basic understanding on the thermodynamic and kinetic aspects of the assembly process paved a path to manipulate these assemblies to meet demands in nanoparticle-based device fabrication and understand structure-property correlations.     

Novel anti-reflection technology for GaAs single-junction solar cells using surface patterning and Au nanoparticles

Single-junction GaAs solar cell structures were grown by low-pressure MOCVD on GaAs (100) substrates. Micro-rod arrays with diameters of 2 microm, 5 microm, and 10 microm were fabricated on the surfaces of the GaAs solar cells via photolithography and wet chemical etching. The patterned surfaces were coated with Au nanoparticles using an Au colloidal solution. Characteristics of the GaAs solar cells with and without the micro-rod arrays and Au nanoparticles were investigated. The short-circuit current density of the GaAs solar cell with 2 microm rod arrays and Au nanoparticles increased up to 34.9% compared to that of the reference cell without micro-rod arrays and Au nanoparticles. The conversion efficiency of the GaAs solar cell that was coated with Au nanoparticles on the patterned surface with micro-rod arrays can be improved from 14.1% to 19.9% under 1 sun AM 1.5G illumination. These results show that micro-rod arrays and Au nanoparticle coating can be applied together in surface patterning to achieve a novel cost-effective anti-reflection technology.     

Self-organized inorganic nanoparticle arrays on protein lattices

Cavities formed by proteins have been utilized as the reaction chamber for the fabrication of a range of inorganic nanoparticles, providing control of the size of particles by limiting growth and preventing agglomeration. In crystal form, proteins construct molecular arrays that can provide regularly arranged sites for nanoparticles. Here we report the fabrication of nanometric iron and indium particles using ferritin, an iron-storage protein. The indium nanoparticles thus formed have uniform spherical shape with diameter of 6.6 +/- 0.5 nm, while the iron nanoparticles are somewhat irregular in shape (5.8 +/- 1.0 nm). Regular two-dimensional arrays of these nanoparticles are successfully produced by crystallizing ferritin molecules on a water-air interface using the denatured protein film method. The lattice constant of these nanoparticle arrays is 13 nm with hexagonal packing, and arrays of more than 1 microm in area can be obtained by transfer onto silicon wafer.     

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.     

Self-organized patterned arrays of Au and Ag nanoparticles by thickness-dependent dewetting of template-confined films

In this work we report on the formation of self-organized and multimodal sized patterned arrays of Au and Ag nanoparticles on SiO₂ surface exploiting the thickness-dependent solid-state dewetting properties of template-confined deposited nanoscale films. In this approach, the Au and Ag surface pattern order, on the SiO₂ substrate, is established by the template confined deposition on a micrometric scale, while the solid-state dewetting phenomenon is induced by thermal processes (below the Au and Ag melting temperature). The deposited films have not an uniform thickness. They, instead, present a controlled thickness due to shadowing mask effects during depositions. Such an inhomogeneity can be further controlled by changing the deposition angle. After the dewetting process, scanning electron microscopy analyses allowed us to correlate the mean diameter 〈D〉 and spacing 〈s〉 of the formed nanoparticles by the thickness h of the deposited films. Despite the dewetting process of the Au and Ag films occurs in the solid state, relations describing the evolution of 〈D〉 and 〈s〉 with 〈h〉 typical of the linear hydrodynamic spinodal dewetting process of liquid films, 〈D〉 ∝ h ^5/3 and 〈s〉 ∝ h ², were verified within a 20 % experimental error. As a consequence we call this process “pseudo-spinodal dewetting”.     

Trimetallic PtCoFe Alloy Monolayer Superlattices as Bifunctional Oxygen‐Reduction and Ethanol‐Oxidation Electrocatalysts

A synthesis strategy for the preparation of trimetallic PtCoFe alloy nanoparticle superlattices is reported. Trimetallic PtCoFe alloy monolayer array of nanoparticle superlattices with a large density of high index facets and platinum‐rich surface are successfully prepared by coreduction of metal precursors in formamide solvent. The concentration of cetyl trimethyl ammonium bromide plays a vital role for the formation of a monolayer array of nanoparticle superlattices, while the size of nanoparticles is determined by NaI. The prepared monolayer array of nanoparticle superlattices is the superior catalyst for oxygen reduction reaction as well as for ethanol oxidation owing to their specific structural and compositional characteristics.     

Generic nanomaterial positioning by carrier and stationary phase design

A generic approach for deploying various types of synthetic nanomaterials, including single-walled carbon nanotubes and nanoparticles, at well-defined locations on substrates is presented. The assembly is achieved through the complementary design of the stationary and carrier phases and utilizes the dewetting process during which polymer-encapsulated nanomaterials are delivered and positioned on predefined locations of substrates. Covalent modification of the nano-objects is not required for the building block positioning, therefore, preserving their intrinsic chemical and physical properties. The potency of this new approach is demonstrated for various synthetic nanomaterials, such as polystyrene, silica, and gold nanoparticles as well as single-walled carbon nanotubes, showing highly specific and direct patterning of cm2 areas using a generic assembly strategy.     

Deterministic Assembly of Single Sub-20 nm Functional Nanoparticles Using a Thermally Modified Template with a Scanning Nanoprobe

A deterministic assembly technique for single sub-20 nm functional nanoparticles is developed based on nanostructured templates fabricated by hot scanning nanoprobes. With this technique, single nanoparticles including quantum dots, polystyrene fluorescent nanobeads, and gold nanoparticles are successfully assembled into 2D arrays with high yields. Experimental and theoretical analyses show that the key for the high yields is the hot-probe-based template fabrication technique, which creates geometrical nanotraps and modifies their surface energy simultaneously. In addition to single nanoparticle patterning, further experiments demonstrate that this technique is also capable of building complex nanostructures, such as nanoparticle clusters with well-defined shapes and heterogeneously integrated nanostructures consisting of quantum dots and silver nanowires. It opens the door to many important applications.     

Three-dimensional assembly of nanoparticles from charged aerosols

The capability of assembling nanoparticles into a desired ordered pattern is a key to realize novel devices which are based not only on the unique properties of nanoparticles but also on the arrangements of nanoparticles. While two-dimensional arrays of nanoparticles have been successfully demonstrated by various techniques, a controlled way of building ordered arrays of three-dimensional (3D) nanoparticle structures remains challenging. We report that a variety of 3D nanoparticle structures can be formed in a controlled way based on the ion-induced focusing, electrical scaffold, and antenna effects from charged aerosols. Particle trajectory calculations successfully predict the whole process of 3D assembly. New surface enhanced Raman scattering substrates based on our 3D assembly were constructed as an example showing the viability of the present approach. This report extends the current capability of positioning nanoparticles on surface to another spatial dimension, which can serve as the foundation of future optical, magnetic, and electronic devices taking the advantage of multidimensions.     

Parallel patterning of nanoparticles via electrodynamic focusing of charged aerosols

The development of nanodevices that exploit the unique properties of nanoparticles will require high-speed methods for patterning surfaces with nanoparticles over large areas and with high resolution. Moreover, the technique will need to work with both conducting and non-conducting surfaces. Here we report an ion-induced parallel-focusing approach that satisfies all requirements. Charged monodisperse aerosol nanoparticles are deposited onto a surface patterned with a photoresist while ions of the same polarity are introduced into the deposition chamber in the presence of an applied electric field. The ions accumulate on the photoresist, modifying the applied field to produce nanoscopic electrostatic lenses that focus the nanoparticles onto the exposed parts of the surface. We have demonstrated that the technique could produce high-resolution patterns at high speed on both conducting (p-type silicon) and non-conducting (silica) surfaces. Moreover, the feature sizes in the nanoparticle patterns were significantly smaller than those in the original photoresist pattern.