M. Serdar Onses

High-resolution patterns of quantum dots formed by electrohydrodynamic jet printing for light-emitting diodes.

Here we demonstrate materials and operating conditions that allow for high-resolution printing of layers of quantum dots (QDs) with precise control over thickness and submicron lateral resolution and capabilities for use as active layers of QD light-emitting diodes (LEDs). The shapes and thicknesses of the QD patterns exhibit systematic dependence on the dimensions of the printing nozzle and the ink composition in ways that allow nearly arbitrary, systematic control when exploited in a fully automated printing tool. Homogeneous arrays of patterns of QDs serve as the basis for corresponding arrays of QD LEDs that exhibit excellent performance. Sequential printing of different types of QDs in a multilayer stack or in an interdigitated geometry provides strategies for continuous tuning of the effective, overall emission wavelengths of the resulting QD LEDs. This strategy is useful to efficient, additive use of QDs for wide ranging types of electronic and optoelectronic devices.

Mechanisms, Capabilities, and Applications of High-Resolution Electrohydrodynamic Jet Printing

This review gives an overview of techniques used for high-resolution jet printing that rely on electrohydrodynamically induced flows. Such methods enable the direct, additive patterning of materials with a resolution that can extend below 100 nm to provide unique opportunities not only in scientific studies but also in a range of applications that includes printed electronics, tissue engineering, and photonic and plasmonic devices. Following a brief historical perspective, this review presents descriptions of the underlying processes involved in the formation of liquid cones and jets to establish critical factors in the printing process. Different printing systems that share similar principles are then described, along with key advances that have been made in the last decade. Capabilities in terms of printable materials and levels of resolution are reviewed, with a strong emphasis on areas of potential application.

Control over Position, Orientation, and Spacing of Arrays of Gold Nanorods Using Chemically Nanopatterned Surfaces and Tailored Particle–Particle–Surface Interactions

The synergy of self- and directed-assembly processes and lithography provides intriguing avenues to fabricate translationally ordered nanoparticle arrangements, but currently lacks the robustness necessary to deliver complex spatial organization. Here, we demonstrate that interparticle spacing and local orientation of gold nanorods (AuNR) can be tuned by controlling the Debye length of AuNR in solution and the dimensions of a chemical contrast pattern. Electrostatic and hydrophobic selectivity for AuNR to absorb to patterned regions of poly(2-vinylpyridine) (P2VP) and polystyrene brushes and mats was demonstrated for AuNR functionalized with mercaptopropane sulfonate (MS) and poly(ethylene glycol), respectively. For P2VP patterns of stripes with widths comparable to the length of the AuNR, single- and double-column arrangements of AuNR oriented parallel and perpendicular to the P2VP line were obtained for MS-AuNR. Furthermore, the spacing of the assembled AuNR was uniform along the stripe and related to the ionic strength of the AuNR dispersion. The different AuNR arrangements are consistent with predictions based on maximization of packing of AuNR within the confined strip.

Inkjet Printing of Regenerated Silk Fibroin: From Printable Forms to Printable Functions.

A formulation of regenerated silk fibroin solution that can be easily functionalized and inkjet printed on numerous surfaces is developed. As an example, the inks can be printed on laboratory gloves that change color when exposed to bacteria.

Block copolymer assembly on nanoscale patterns of polymer brushes formed by electrohydrodynamic jet printing.

Fundamental understanding of the self-assembly of domains in block copolymers (BCPs) and capabilities in control of these processes are important for their use as nanoscale templates in various applications. This paper focuses on the self-assembly of spin-cast and printed poly(styrene-block-methyl methacrylate) BCPs on patterned surface wetting layers formed by electrohydrodynamic jet printing of random copolymer brushes. Here, end-grafted brushes that present groups of styrene and methyl methacrylate in geometries with nanoscale resolution deterministically define the morphologies of BCP nanostructures. The materials and methods can also be integrated with lithographically defined templates for directed self-assembly of BCPs at multiple length scales. The results provide not only engineering routes to controlled formation of complex patterns but also vehicles for experimental and simulation studies of the effects of chemical transitions on the processes of self-assembly. In particular, we show that the methodology developed here provides the means to explore exotic phenomena displayed by the wetting behavior of BCPs, where 3-D soft confinement, chain elasticity, interfacial energies, and substrates surface energy cooperate to yield nonclassical wetting behavior.

Highly Selective Immobilization of Au Nanoparticles onto Isolated and Dense Nanopatterns of Poly(2-vinyl pyridine) Brushes down to Single-Particle Resolution

Chemical patterns consisting of poly(2-vinyl pyridine) (P2VP) brushes in a background of a cross-linked polystyrene (PS) mat enabled the highly selective placement of citrate-stabilized Au nanoparticles (NPs) in arrays on surfaces. The cross-linked PS mat prevented the nonspecific binding of Au NPs, and the regions functionalized with P2VP brushes allowed the immobilization of the particles. Isolated chemical patterns of feature sizes from hundreds to tens of nanometers were prepared by standard lithographic techniques. The number of 13 nm Au NPs bound per feature increased linearly with increasing area of the patterns. This behavior is similar to previous reports using 40 nm particles or larger. Arrays of single NPs were obtained by reducing the dimensions of patterned P2VP brushes to below ~20 nm. To generate dense (center-to-center distance = 80 nm) linear chemical patterns for the placement of rows of single NPs, a block-copolymer (BCP)-assisted lithographic process was used. BCPs healed defects associated with the standard lithographic patterning of small dimensions at high densities and led to highly registered, linear, single NP arrays.

Tunable Assembly of Gold Nanoparticles on Nanopatterned Poly(ethylene glycol) Brushes

The organization of metallic nanoparticles (NPs) into ordered arrays on nanopatterned surfaces is an enabling process to fabricate devices and study the properties of the particles. Tailoring the interaction between NPs and nanopatterns is a necessity to gain a high level of control in this process. Here, nanopatterned poly(ethylene glycol) (PEG) brushes are presented as a platform for the organization of Au NPs on surfaces. The binding of citrate-stabilized Au NPs to the PEG brushes depends on the size of the particles and molecular weight of the brushes: the density of NPs immobilized on the nanopatterns of PEG brushes increases with decreasing the diameter of the particles and increasing the chain length of the brushes. The key aspect of the process is to pattern PEG brushes with high resolution and chemical contrast to provide controllable and specific interaction between Au NPs and nanopatterns at a single particle resolution. The modulation of the number (0-4) of Au NPs (e.g., 30 nm) per patterned feature with a high level of accuracy and the generation of patterned heterostructures that consist of two different sizes (e.g., 40 and 20 nm) of particles constitute two examples showing the capabilities of the presented platform.

Localization of multiple DNA sequences on nanopatterns.

DNA oligonucleotides of different sequences were patterned at the nanoscale. Areas of positive charge were generated by exposure of insulating substrates, spin-on hydrogen silsesquioxane or vapor-deposited SiO(2) on Si, with ionizing radiation sources used in electron beam and extreme ultraviolet lithography. Au nanoparticles (NPs) with a diameter of 15 nm, carrying covalently bound negatively charged single-stranded DNA oligonucleotides, were site specifically immobilized directly on the exposed regions and presented oligonucleotides for subsequent hybridization. Repeated exposure and deposition of NPs allowed for patterning multiple DNA sequences. Patterns with dimensions as small as 15 nm were fabricated using electron beam lithography. The use of DNA-functionalized NPs rather than just DNA facilitates metrology in scanning electron microscopy and improves the hybridization efficiency of the oligonucleotides on the surface.

Fabrication of nanopatterned poly(ethylene glycol) brushes by molecular transfer printing from poly(styrene-block-methyl methacrylate) films to generate arrays of Au nanoparticles.

This article presents a soft lithographic approach using block copolymer (BCP) films to fabricate functional chemically patterned polymer brushes on the nanoscale. Hydroxyl-terminated poly(ethylene glycol) (PEG-OH) was transfer printed from the poly(methyl methacrylate) (PMMA) domains of self-assembled poly(styrene-block-methyl methacrylate) films to a substrate in conformal contact with the film to generate patterned PEG brushes mirroring the pattern of BCP domains. A key point in the study is that the chemistry of the functional transferred brushes is different from the chemistry of either block of the copolymer; PEG-OH is miscible only in the PMMA block and therefore transferred only from PMMA domains. The functionality of the PEG brushes was demonstrated by the selective immobilization of citrate-stabilized Au NPs (15 nm) and validated the generation of high-quality chemical patterns with sub-30-nm feature sizes.

Nanometer Scale Alignment of Block‐Copolymer Domains by Means of a Scanning Probe Tip

Alignment of perpendicularly oriented lamellar block copolymer domains using an AFM tip is demonstrated. The AFM tip orients the domains through local shearing, resulting in domain alignment parallel to tip travel. AFM tips can also deposit block copolymer nanostructures on heated substrates with a variety of experimentally observed domain alignments.