Self-organization and dewetting kinetics in sub-10 nm diblock copolymer line/space lithography.

In this work, we investigated the self-assembly of a lamellar block copolymer (BCP) under different wetting conditions. We explored the influence of the chemical composition of under-layers and top-coats on the thin film stability, self-assembly kinetics and BCP domain orientation. Three different chemistries were chosen for these surface affinity modifiers and their composition was tuned in order to provide either neutral wetting (i.e. an out-of-plane lamellar structure), or affine wetting conditions (i.e. an in-plane lamellar structure) with respect to a sub-10 nm PS-b-PDMSB lamellar system. Using such controlled wetting configurations, the competition between the dewetting of the BCP layer and the self-organization kinetics was explored. We also evaluated the spreading parameter of the BCP films with respect to the configurations of surface-energy modifiers and demonstrated that BCP layers are intrinsically unstable to dewetting in a neutral configuration. Finally, the dewetting mechanisms were evaluated with respect to the different wetting configurations and we clearly observed that the rigidity of the top-coat is a key factor to delay BCP film instability.

Lithographically Defined Cross-Linkable Top Coats for Nanomanufacturing with High-χ Block Copolymers.

The directed self-assembly (DSA) of block copolymers (BCPs) is a powerful method for the manufacture of high-resolution features. Critical issues remain to be addressed for successful implementation of DSA, such as dewetting and controlled orientation of BCP domains through physicochemical manipulations at the BCP interfaces, and the spatial positioning and registration of the BCP features. Here, we introduce novel top-coat (TC) materials designed to undergo cross-linking reactions triggered by thermal or photoactivation processes. The cross-linked TC layer with adjusted composition induces a mechanical confinement of the BCP layer, suppressing its dewetting while promoting perpendicular orientation of BCP domains. The selection of areas of interest with perpendicular features is performed directly on the patternable TC layer via a lithography step and leverages attractive integration pathways for the generation of locally controlled BCP patterns and nanostructured BCP multilayers.

An embedded neutral layer for advanced surface affinity control in grapho-epitaxy directed self-assembly.

Advanced surface affinity control for grapho-epitaxy directed self-assembly (DSA) patterning is essential for providing reliable DSA-based solutions for the development of semiconductor patterning. Independent control of surface affinity between the bottom and the sidewalls of a topographical guiding structure was achieved by embedding an ultrathin layer in the guiding template stack. The implementation of an embedded layer with tunable surface properties for DSA grapho-epitaxy was evaluated and optimized on 300 mm wafers by critical dimension SEM characterization. It was demonstrated that a thin protective layer, placed between the hard mask guiding template and the embedded layer, allows the preservation of the surface properties of the embedded layer during guiding template etching. The DSA performances of this novel grapho-epitaxy integration, using a topographical template patterned with 193 nm immersion lithography, were evaluated by monitoring the success rate and the critical dimension uniformity of the shrunk contacts. FIB-STEM analyses were further carried out to analyze the residual polymer thickness on the resulting contacts. This new integration leads to the control of the polymer residual thickness (a few nanometers) and uniformity (inferior to 1 nm) at the bottom of the guiding template which will facilitate the subsequent DSA pattern transfer.

Straightforward Integration Flow of a Silicon-Containing Block Copolymer for Line-Space Patterning.

A promising alternative for the next-generation lithography is based on the directed self-assembly of block copolymers (BCPs) used as a bottom-up tool for the definition of nanometric features. Herein, a straightforward integration flow for line-space patterning is reported for a silicon BCP system, that is, poly(1,1-dimethylsilacyclobutane)-b-poly(styrene) (PDMSB-b-PS), able to define sub 15 nm features. Both in-plane cylindrical (L0 = 20.7 nm) and out-of-plane lamellar structures (L0 = 23.2 nm) formed through a rapid thermal annealing-10 min at 180 °C-were successfully integrated using graphoepitaxy to provide a long-range ordering of the BCP structure without the use of underlayers or top coats. Subsequent deep transfer into the silicon substrate using the hardened oxidized PDMSB domains as a mask is demonstrated. Combining a rapid self-assembly behavior, straightforward integration, and an excellent etching contrast, PDMSB-b-PS may become a material of choice for the next-generation lithography.

Assessing the Local Nanomechanical Properties of Self-Assembled Block Copolymer Thin Films by Peak Force Tapping.

The mechanical properties of several types of block copolymer (BCP) thin films have been investigated using PeakForce quantitative nanomechanical mapping. The samples consisted of polystyrene/poly(methylmethacrylate) (PS/PMMA)-based BCP thin films with different pitches both randomly oriented and self-assembled. The measured films have a critical thickness below 50 nm and present features to be resolved of less than 22 nm. Beyond measuring and discriminate surface elastic modulus and adhesion forces of the different phases, we tuned the peak force parameters in order to reliably image those samples, avoiding plastic deformation. The method is able to detect the changes in mechanical response associated with the orientation of the PMMA cylinders with respect to the substrate (parallel versus vertical). The nanomechanical investigation is also capable of recognizing local stiffening due to the preferential growth of alumina deposited by atomic layer deposition on BCP samples, opening up new possibilities in the field of hard mask materials characterization.

Sub-10 nm features obtained from directed self-assembly of semicrystalline polycarbosilane-based block copolymer thin films.

Highly-ordered arrays with sub-10 nm features are produced with topographical-directed self-assembly of low-molecular-weight poly(1,1-dimethyl silacyclobutane)-block-poly(methyl methacrylate). This system turns out to be of high interest for lithographic applications since the domain orientation is solely controlled through the polymer layer thickness, while the promotion of the microphase separation is obtained by a short thermal annealing process under mild conditions.

Nanoscale block copolymer ordering induced by visible interferometric micropatterning: a route towards large scale block copolymer 2D crystals.

We have overcome the cost and time consumption limitations of common lithography techniques used to control the self-assembly of block copolymers into highly ordered 2D arrays through the use of a guiding pattern created from a polymeric sub-layer. The guiding pattern is a sinusoidal surface-relief grating interferometrically inscribed onto an azobenzene containing copolymer sub-layer leading to a defect-free single grain of block copolymer domains.