Nanorod position and orientation in vertical cylinder block copolymer films.

The self-assembly of gold nanorods (AuNRs) of different sizes with a block copolymer (BCP) is studied. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films containing P2VP functionalized AuNRs are solvent annealed resulting in a BCP morphology of vertical P2VP cylinders in a PS matrix. At the surface of the PS-b-P2VP films long AuNRs are found in the bridging and vertical states. The bridging state is where the long axis of the AuNR is parallel to the film surface, the AuNR is embedded in the film, and each end of the AuNR is at the top of nearest neighbor P2VP cylinders. The vertical state is where the AuNR is localized within a vertical P2VP cylinder, the AuNR long axis is perpendicular to the film surface and the upper tip of the AuNR is at the film surface. Short AuNRs were found in the bridging and vertical states as well as in a state not observed for the long AuNRs, the centered state. The centered state is where an AuNR has its long axis parallel to the film surface, is embedded in the film, and is centered over a vertical P2VP cylinder. Hybrid particle-field theory (HPFT) simulations modeling the experimental system predict that for the long AuNRs only the bridging state should be observed while for the short AuNRs only the bridging and centered states should be observed. Possible explanations for why the vertical state is observed in experiments despite being thermodynamically unfavorable in simulations are discussed. HPFT simulations also show that when a nanorod is in the bridging state the two cylinders it bridges remain intact and extend from the nanorod to the substrate. Further, the minority block of the BCP is shown to wet the bottom of the bridging nanorod. The bridging state is very promising for the future development of self-assembled nanoscale devices.

Kinetic Monitoring of Block Copolymer Self-Assembly Using In Situ Spectroscopic Ellipsometry.

Understanding the kinetic pathways of self-assembly in block copolymers (BCPs) has been a long-standing challenge, mostly due to limitations of in situ monitoring techniques. Here, we demonstrate an approach that uses optical birefringence, determined by spectroscopic ellipsometry (SE), as a measure of domain formation in cylinder- and lamellae-forming BCP films. The rapid experimental acquisition time in SE (ca. 1 sec) enables monitoring of the assembly/disassembly kinetics of BCP films during solvent-vapor annealing (SVA). We demonstrate that upon SVA, BCP films form ordered domains that are stable in the swollen state, but disorder upon rapid drying. Surprisingly, the disassembly during drying strongly depends on the duration of solvent exposure in the swollen state, explaining previous observations of loss of order in SVA processes. SE thus allows for decoupling of BCP self-assembly and disordering that occurs during solvent annealing and solvent evaporation, which is difficult to probe using other, slower techniques.

Dispersion and alignment of nanorods in cylindrical block copolymer thin films.

Although significant progress has been made in controlling the dispersion of spherical nanoparticles in block copolymer thin films, our ability to disperse and control the assembly of anisotropic nanoparticles into well-defined structures is lacking in comparison. Here we use a combination of experiments and field theoretic simulations to examine the assembly of gold nanorods (AuNRs) in a block copolymer. Experimentally, poly(2-vinylpyridine)-grafted AuNRs (P2VP-AuNRs) are incorporated into poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) thin films with a vertical cylinder morphology. At sufficiently low concentrations, the AuNRs disperse in the block copolymer thin film. For these dispersed AuNR systems, atomic force microscopy combined with sequential ultraviolet ozone etching indicates that the P2VP-AuNRs segregate to the base of the P2VP cylinders. Furthermore, top-down transmission electron microscopy imaging shows that the P2VP-AuNRs mainly lie parallel to the substrate. Our field theoretic simulations indicate that the NRs are strongly attracted to the cylinder base where they can relieve the local stretching of the minority block of the copolymer. These simulations also indicate conditions that will drive AuNRs to adopt a vertical orientation, namely by increasing nanorod length and/or reducing the wetting of the short block towards the substrate.

A cantilever-free approach to dot-matrix nanoprinting.

Scanning probe lithography (SPL) is a promising candidate approach for desktop nanofabrication, but trade-offs in throughput, cost, and resolution have limited its application. The recent development of cantilever-free scanning probe arrays has allowed researchers to define nanoscale patterns in a low-cost and high-resolution format, but with the limitation that these are duplication tools where each probe in the array creates a copy of a single pattern. Here, we report a cantilever-free SPL architecture that can generate 100 nanometer-scale molecular features using a 2D array of independently actuated probes. To physically actuate a probe, local heating is used to thermally expand the elastomeric film beneath a single probe, bringing it into contact with the patterning surface. Not only is this architecture simple and scalable, but it addresses fundamental limitations of 2D SPL by allowing one to compensate for unavoidable imperfections in the system. This cantilever-free dot-matrix nanoprinting will enable the construction of surfaces with chemical functionality that is tuned across the nano- and macroscales.

Plow and ridge nanofabrication.

Traditionally, scanning probe lithography tools are limited in resolution by the radius of curvature of the tip used. Herein, an approach is described for patterning the ridge of piled-up polymer that naturally occurs when a scanning probe is pressed against a soft surface. The use of this phenomenon to transfer patterns to hard materials with 20 nm resolution is demonstrated.

Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces.

Although nanoparticles with exquisite properties have been synthesized for a variety of applications, their incorporation into functional devices is challenging owing to the difficulty in positioning them at specified sites on surfaces. In contrast with the conventional synthesis-then-assembly paradigm, scanning probe block copolymer lithography can pattern precursor materials embedded in a polymer matrix and synthesize desired nanoparticles on site, offering great promise for incorporating nanoparticles into devices. This technique, however, is extremely limited from a materials standpoint. To develop a materials-general method for synthesizing nanoparticles on surfaces for broader applications, a mechanistic understanding of polymer-mediated nanoparticle formation is crucial. Here, we design a four-step synthetic process that enables independent study of the two most critical steps for synthesizing single nanoparticles on surfaces: phase separation of precursors and particle formation. Using this process, we elucidate the importance of the polymer matrix in the diffusion of metal precursors to form a single nanoparticle and the three pathways that the precursors undergo to form nanoparticles. Based on this mechanistic understanding, the synthetic process is generalized to create metal (Au, Ag, Pt, and Pd), metal oxide (Fe(2)O(3), Co(2)O(3), NiO, and CuO), and alloy (AuAg) nanoparticles. This mechanistic understanding and resulting process represent a major advance in scanning probe lithography as a tool to generate patterns of tailored nanoparticles for integration with solid-state devices.

Multifunctional cantilever-free scanning probe arrays coated with multilayer graphene.

Scanning probe instruments have expanded beyond their traditional role as imaging or "reading" tools and are now routinely used for "writing." Although a variety of scanning probe lithography techniques are available, each one imposes different requirements on the types of probes that must be used. Additionally, throughput is a major concern for serial writing techniques, so for a scanning probe lithography technique to become widely applied, there needs to be a reasonable path toward a scalable architecture. Here, we use a multilayer graphene coating method to create multifunctional massively parallel probe arrays that have wear-resistant tips of uncompromised sharpness and high electrical and thermal conductivities. The optical transparency and mechanical flexibility of graphene allow this procedure to be used for coating exceptionally large, cantilever-free arrays that can pattern with electrochemical desorption and thermal, in addition to conventional, dip-pen nanolithography.

Three-dimensionally-patterned submicrometer-scale hydrogel/air networks that offer a new platform for biomedical applications.

Phase mask interference lithography was employed to fabricate three-dimensional (3D) hydrogel structures with high surface area on neural prosthetic devices. A random terpolymer of poly(hydroxyethyl methacrylate- ran-methyl methacrylate- ran-methacrylic acid) was synthesized and used as a negative-tone photoresist to generate bicontinuous 3D hydrogel structures at the submicrometer scale. We demonstrated that the fully open 3D hydrogel/air networks can be used as a pH-responsive polymeric drug-release system for the delivery of neurotrophins to enhance the performance of neural prosthetic devices. Additionally an open hydrogel structure will provide direct access of neuronal growth to the device for improved electrical coupling.