Christopher J. Thode

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.

Implementation of a chemo-epitaxy flow for directed self-assembly on 300-mm wafer processing equipment

Abstract. The implementation of our previously reported chemo-epitaxy method for directed self-assembly (DSA) of block copolymers (BCPs) on 300-mm wafers is described in detail. Some challenges to be addressed include edge bead removal control of the layers forming the exposure stack and uniformity of the deposited films across the wafer. With the fine tuning of the process conditions, this flow provides chemically nanopatterned substrates with well-defined geometry and chemistry. After a film of BCP is annealed on the chemical patterns, high degrees of perfection are achieved. A BCP with natural periodicity of 25 nm was assembled on100-nm pitch prepatterns, obtaining 4X feature multiplication. Top-down scanning electron microscope images show a wide process window with depth of focus >200  nm and exposure latitude >40% for lines and spaces of 12.5-nm half-pitch. We provide a platform for future study of the origin of DSA generated defects and their relationship to process conditions and materials that are amenable to use by the semiconductor industry.

Towards an all-track 300 mm process for directed self-assembly

This study modifies the authors’ previously reported directed self-assembly (DSA) process of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in order to meet the throughput and material-related requirements of a semiconductor manufacturing environment. It is demonstrated that all of the bottleneck steps in the authors’ DSA process, including the deposition of the cross-linkable mat and the deposition of the brush layer, can be done in minutes on a hot plate in an N2 atmosphere, which simulates the processing environment of a lithography track module. A 25-nm-pitch pattern resulting from a 4:1 density multiplication was demonstrated with a manufacturing-compatible organic solvent. A preliminary uniformity study on 300 mm wafers was also presented. The modified DSA process presents a viable solution to some of the anticipated throughput-related challenges to DSA commercialization and thus, brings integration of DSA within reach of the semiconductor manufacturing industry.

All track directed self-assembly of block copolymers: process flow and origin of defects

Directed Self-Assembly (DSA) of block copolymers is considered to be a potential lithographic solution to achieve higher feature densities than can be obtained by current lithographic techniques. However, it is still not well-established how amenable DSA of block copolymers is to an industrial fabrication environment in terms of defectivity and processing conditions. Beyond production-related challenges, precise manipulation of the geometrical and chemical properties over the substrate is essential to achieve high pattern fidelity upon the self-assembly process. Using our chemo-epitaxy DSA approach offers control over the surface properties of the slightly preferential brush material as well as those of the guiding structures. This allows for a detailed assessment of the critical material parameters for defect reduction. The precise control of environment afforded by industrial equipment allows for the selective analysis of material and process related boundary conditions and assessment of their effect on defect generation. In this study, the previously reported implementation of our feature multiplication process was used to investigate the origin of defects in terms of the geometry of the initial pre-patterns. Additionally, programmed defects were used to investigate the ability of the BCP to heal defects in the resist patterns and will aid to assess the capture capability of the inspection tool. Finally, the set-up of the infrastructure that will allow the study the generation of defects due to the interaction of the BCP with the boundary conditions has been accomplished at imec.

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.

Demonstration of glass transition temperature shift in thin supported polystyrene films by internal reference method

An internal reference method is used for the first time to clearly demonstrate the glass transition temperature (Tg) depression effect in 5 nm thick polystyrene films spin-cast on silicon wafers. Initially flat films exhibit depressed Tg at approximately 85 °C. Temperature-induced dewetting on hexamethyldisilazane-treated silicon substrates leads to formation of discontinuous films with average effective thickness of 15-30 nm. Dewetted films demonstrate Tg close to the bulk value (≈ 100 °C) and are used as internal references. Data both for continuous and discontinuous films are obtained in the same experimental run for the same sample, which allows direct comparison between datasets. Phase-modulated ellipsometry in vacuum is used to monitor glass transition. Both traditional linear temperature scan method and a novel temperature modulated technique have been employed in the measurements.