Controlled Molecular Assembly via Dynamic Confinement of Solvent.

Assembly from ultrasmall solution droplets follows a different dynamic from that of larger scales. Using an independently controlled microfluidic probe in an atomic force microscope, subfemtoliter aqueous droplets containing polymers produce well-defined features with dimensions as small as tens of nanometers. The initial shape of the droplet and the concentration of solute within the droplet play significant roles in the final assembly of polymers due to the ultrafast evaporation rate and spatial confinement by the small droplets. These effects are used to control the final molecular assembly in terms of feature geometry and distribution and packing of individual molecules within the features. This work introduces new means of control over molecular assembly, bringing us closer to programmable synthesis for chemistry and materials science. The outcomes pave the way for three-dimensional (3D) nanoprinting in additive manufacturing.

Three-Dimensional Nanoprinting via Direct Delivery.

Direct writing methods are a generic and simple means to produce designed structures in three dimensions (3D). The printing is achieved by extruding printing materials through a nozzle, which provides a platform to deliver a wide range of materials. Although this method has been routinely used for 3D printing at macroscopic scales, miniaturization to micrometer and nanometer scales and building hierarchical structures at multidimensional scales represent new challenges in research and development. The current work addresses these challenges by combining the spatial precision of atomic force microscopy (AFM) and local delivery capability of microfluidics. Specialized AFM probes serve dual roles of a microscopy tip and a delivery tool, enabling the miniaturization of 3D printing via direct material delivery. Stacking grids of 20 µm periodicity were printed layer-by-layer covering 1 mm × 1 mm regions. The spatial fidelity was measured to be several nanometers, which is among the highest in 3D printing. The results clearly demonstrate the feasibility of achieving high precision 3D nanoprinting with nanometer feature size and accuracy with practical throughput and overall size. This work paves the way for advanced applications of 3D hierarchical nanostructures.

Three-Dimensional Nanoprinting via Scanning Probe Lithography-Delivered Layer-by-Layer Deposition.

Three-dimensional (3D) printing has been a very active area of research and development due to its capability to produce 3D objects by design. Miniaturization and improvement of spatial resolution are major challenges in current 3D printing technology development. This work reports advances in miniaturizing 3D printing to the nanometer scale using scanning probe microscopy in conjunction with local material delivery. Using polyelectrolyte polymers and complexes, we have demonstrated the concept of layer-by-layer nanoprinting by design. Nanometer precision is achieved in all three dimensions, as well as in interlayer registry. The approach enables production of designed functional 3D materials with nanometer resolution and, as such, creates a platform for conducting scientific research in designed 3D nanoenvironments as well. In doing so, it enables production of nanomaterials and scaffolds for photonics devices, biomedicine, and tissue engineering.

Nanoscale chemical imaging by photoinduced force microscopy.

Correlating spatial chemical information with the morphology of closely packed nanostructures remains a challenge for the scientific community. For example, supramolecular self-assembly, which provides a powerful and low-cost way to create nanoscale patterns and engineered nanostructures, is not easily interrogated in real space via existing nondestructive techniques based on optics or electrons. A novel scanning probe technique called infrared photoinduced force microscopy (IR PiFM) directly measures the photoinduced polarizability of the sample in the near field by detecting the time-integrated force between the tip and the sample. By imaging at multiple IR wavelengths corresponding to absorption peaks of different chemical species, PiFM has demonstrated the ability to spatially map nm-scale patterns of the individual chemical components of two different types of self-assembled block copolymer films. With chemical-specific nanometer-scale imaging, PiFM provides a powerful new analytical method for deepening our understanding of nanomaterials.

High-throughput directed self-assembly of core-shell ferrimagnetic nanoparticle arrays.

Magnetic nanoparticles (MNPs) provide a set of building blocks for constructing stimuli-responsive nanoscale materials with properties that are unique to this scale. The size and the composition of MNPs are tunable to meet the requirements for a range of applications including biosensors and data storage. Although many of these technologies would significantly benefit from the organization of nanoparticles into higher-order architectures, the precise placement and arrangement of nanoparticles over large areas of a surface remain a challenge. Herein, we demonstrate the viability of magnetic nanoparticles for patterned recording media utilizing a template-directed self-assembly process to afford well-defined nanostructures of magnetic nanoparticles and access these assemblies using magnetic force microscopy and a magnetic recording head. Photolithographically defined holes were utilized as templates to form assemblies of ferrimagnetic nanoparticle rings or pillars selectively over a large area (>1 cm(2)) in just 30 s. This approach is applicable to other nanoparticle systems as well and enables their high-throughput self-assembly for future advanced device fabrication.

Broad-spectrum antimicrobial supramolecular assemblies with distinctive size and shape.

With the increased prevalence of antibiotic-resistant infections, there is an urgent need for innovative antimicrobial treatments. One such area being actively explored is the use of self-assembling cationic polymers. This relatively new class of materials was inspired by biologically pervasive cationic host defense peptides. The antimicrobial action of both the synthetic polymers and naturally occurring peptides is believed to be complemented by their three-dimensional structure. In an effort to evaluate shape effects on antimicrobial materials, triblock polymers were polymerized from an assembly directing terephthalamide-bisurea core. Simple changes to this core, such as the addition of a methylene spacer, served to direct self-assembly into distinct morphologies-spheres and rods. Computational modeling also demonstrated how subtle core changes could directly alter urea stacking motifs manifesting in unique multidirectional hydrogen-bond networks despite the vast majority of material consisting of poly(lactide) (interior block) and cationic polycarbonates (exterior block). Upon testing the spherical and rod-like morphologies for antimicrobial properties, it was found that both possessed broad-spectrum activity (Gram-negative and Gram-positive bacteria as well as fungi) with minimal hemolysis, although only the rod-like assemblies were effective against Candida albicans.

Self-assembled ferrimagnet--polymer composites for magnetic recording media.

A self-assembled magnetic recording medium was created using colloidal ferrimagnetic building blocks. Monodisperse cobalt ferrite nanoparticles (CoFe(2)O(4)) were synthesized using solution-based methods and then stabilized in solution using the amphiphilic diblock copolymer, poly(acrylic acid)-b-poly(styrene) (PAA-PS). The acid groups of the acrylate block bound the polymer to the nanoparticle surface via multivalent interactions, while the styrene block afforded the magnetic nanoparticle--polymer complex solubility in organic solvents. Moreover, the diblock copolymer improved the colloidal stability of the ferrimagnetic CoFe(2)O(4) nanoparticles by reducing the strong interparticle magnetic interactions, which typically caused the ferrimagnetic nanoparticles to irreversibly aggregate. The nanoparticle--polymer complex was spin-coated onto a silicon substrate to afford self-organized thin film arrays, with the interparticle spacing determined by the molecular weight of the diblock copolymer. The thin film composite was also exposed to an external magnetic field while simultaneously heated above the glass transition temperature of poly(styrene) to allow the nanoparticles to physically rotate to align their easy axes with the direction of the magnetic field. In order to demonstrate that this self-assembled ferrimagnet--polymer composite was suitable as a magnetic recording media, read/write cycles were demonstrated using a contact magnetic tester. This work provides a simple route to synthesizing stabilized ferrimagnetic nanocrystals that are suitable for developing magnetic recording media.

Nanoscale three-dimensional patterning of molecular resists by scanning probes.

For patterning organic resists, optical and electron beam lithography are the most established methods; however, at resolutions below 30 nanometers, inherent problems result from unwanted exposure of the resist in nearby areas. We present a scanning probe lithography method based on the local desorption of a glassy organic resist by a heatable probe. We demonstrate patterning at a half pitch down to 15 nanometers without proximity corrections and with throughputs approaching those of Gaussian electron beam lithography at similar resolution. These patterns can be transferred to other substrates, and material can be removed in successive steps in order to fabricate complex three-dimensional structures.

Placement and orientation of individual DNA shapes on lithographically patterned surfaces.

Artificial DNA nanostructures show promise for the organization of functional materials to create nanoelectronic or nano-optical devices. DNA origami, in which a long single strand of DNA is folded into a shape using shorter 'staple strands', can display 6-nm-resolution patterns of binding sites, in principle allowing complex arrangements of carbon nanotubes, silicon nanowires, or quantum dots. However, DNA origami are synthesized in solution and uncontrolled deposition results in random arrangements; this makes it difficult to measure the properties of attached nanodevices or to integrate them with conventionally fabricated microcircuitry. Here we describe the use of electron-beam lithography and dry oxidative etching to create DNA origami-shaped binding sites on technologically useful materials, such as SiO(2) and diamond-like carbon. In buffer with approximately 100 mM MgCl(2), DNA origami bind with high selectivity and good orientation: 70-95% of sites have individual origami aligned with an angular dispersion (+/-1 s.d.) as low as +/-10 degrees (on diamond-like carbon) or +/-20 degrees (on SiO(2)).

Monolayered organosilicate toroids and related structures: A phase diagram for templating from block copolymers.

Here we report the controlled generation of micelle-templated organosilicate nanostructures resulting from self-assembly of a block copolymer/organosilicate mixture followed by organosilicate vitrification and copolymer thermolysis. Variation of solution condition and the copolymer/organosilicate mixture composition generates widely different film morphologies ranging from toroids to linear features to contiguous nanoporous monolayers. The use of reactive organosilicates for block copolymer templation generates functional inorganic nanostructures with thermal and mechanical stability.

Atomically flat gold on elastomeric substrate.

We present a procedure to fabricate extremely smooth Au films supported on thin elastomeric (PDMS) substrates. Minimum rms roughness and largest grain size are obtained using Si wafers, coated with native oxide and release layers, as templates for the growth of thermally evaporated Au films. The wafers are held at a temperature of 300 degrees C during deposition. The Au films, up to 200 nm thick, are then transferred onto poly(dimethylsiloxane) substrates which have been previously surface-functionalized with a (3-mercaptopropyl)trimethoxysilane adhesion layer. The resulting Au films have been found by AFM to be extremely smooth with rms-roughness 2.5-4 angstroms and to exhibit a crystalline morphology with flat grains >500 nm in size. Thinner films, down to 20 nm, are grown at lower temperature and are comparably smooth, but with a loss in crystalline morphology. We compare the results of this optimized procedure with other gold films grown on mica sheets as templates and to those produced using Ti-O-Si interfacial chemistry.

Patterned polyfluorene surfaces by functionalization of nanoimprinted polymeric features.

A new procedure is described for surface grafting polymer brushes by step-growth polymerization from initiator-embedded polymeric thin films and micron- and nanometer-scale patterns. An imprint lithographic process, nanocontact molding, was used to prepare thin patterned cross-linked polyacrylate network films on silicon wafers that incorporated 4-bromostyrene in the networks. These networks present reactive 4-bromophenyl functionality at the surface that act as attachment sites for the subsequent Ni(0)- mediated step-growth condensation polymerization of 2,7-dibromo-9,9-dihexylfluorene The step-growth polymerization medium consisted of 2,7-dibromo-9,9-dihexylfluorene, Ni(0)-catalyst, and bipyridine in a toluene/dimethylformamide solvent mixture. The resulting growth of polydihexylfluorene brushes from the patterned surface was monitored by contact angle, optical spectrometry, surface profilometry and AFM. Brush growth was conducted from patterned features ranging from 100 microm to 100 nm in width and 50 nm in height. The optical and fluorescence behavior of the polyfluorene brushes was similar to that of thin polyfluorene films made by spin coating.

Controlling nanowear in a polymer by confining segmental relaxation.

Molecular relaxation of a copolymer designed for nano-electromechanical systems was chemically confined by varying the spacing between cross-links, delta(c). A critical cross-link spacing of 1-3 nm marks a transition in the nano-mechanical properties evaluated by atomic force microscopy. The transition reveals an interplay between the cross-link spacing and the length scale for backbone relaxation, xi(alpha), in cooperatively rearranging regions. For delta(c) >> xi(alpha), the natural backbone relaxation process is relatively unaffected by the cross-links and a ductile, low hardness behavior results. For delta(c) < xi(alpha), the cross-links directly interfere with backbone relaxation and confine segmental mobility, leading to a brittle, high hardness response.

Interfacial glass transition profiles in ultrathin, spin cast polymer films.

Interfacial glass transition temperature (T(g)) profiles in spin cast, ultrathin films of polystyrene and derivatives were investigated using shear-modulated scanning force microscopy. The transitions were measured as a function of film thickness (delta), molecular weight, and crosslinking density. The T(g)(delta) profiles were nonmonotonic and exhibited two regimes: (a) a sublayer extending about 10 nm from the substrate, with T(g) values lowered up to approximately 10 degrees C below the bulk value, and (b) an intermediate regime extending over 200 nm beyond the sublayer, with T(g) values exceeding the bulk value by up to 10 degrees C. Increasing the molecular weight was found to shift the T(g)(delta) profiles further from the substrate interface, on the order of 10 nm/kDa. Crosslinking the precast films elevated the absolute T(g) values, but had no effect on the spatial length scale of the T(g)(delta) profiles. These results are explained in the context of film preparation history and its influence on molecular mobility. Specifically, the observed rheological anisotropy is interpreted based on the combined effects of shear-induced structuring and thermally activated interdiffusion.