Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocks of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. The ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications.

PMMA (poly(styrene-block-methyl methacrylate)) block copolymer and sequential infiltration synthesis (SIS). A key advance relates to the use of PMMA majority block copolymer films and the optimization of thermal annealing temperature and substrate chemistry to achieve through-film vertical PS cylinders. The resulting morphology allows for direct fabrication of nanoporous AlOx by selective growth of Al2O3 in the PMMA matrix during the SIS process, followed by polymer removal using oxygen plasma. Control over the pore diameter is achieved by varying the number of Al2O3 growth cycles, leading to pore size reduction from 21 nm to 16 nm. Three-dimensional characterization, using TEM tomography, reveals that the AlOx channels are continuous through the film and have a gradual increase in pore size with depth. Finally, we demonstrate the ultrafiltration performance of the fabricated AlOx membrane for protein separation as a function of protein size and charge.

Understanding and controlling the three-dimensional structure of block copolymer (BCP) thin films is critical for utilizing these materials for sub-20 nm nanopatterning in semiconductor devices, as well as in membranes and solar cell applications. Combining an atomic layer deposition (ALD)-based technique for enhancing the contrast of BCPs in transmission electron microscopy (TEM) together with scanning TEM (STEM) tomography reveals and characterizes the three-dimensional structures of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) thin films with great clarity. Sequential infiltration synthesis (SIS), a block-selective technique for growing inorganic materials in BCPs films in an ALD tool and an emerging technique for enhancing the etch contrast of BCPs, was harnessed to significantly enhance the high-angle scattering from the polar domains of BCP films in the TEM. The power of combining SIS and STEM tomography for three-dimensional (3D) characterization of BCP films was demonstrated with the following cases: self-assembled cylindrical, lamellar, and spherical PS-b-PMMA thin films. In all cases, STEM tomography has revealed 3D structures that were hidden underneath the surface, including (1) the 3D structure of defects in cylindrical and lamellar phases, (2) the nonperpendicular 3D surface of grain boundaries in the cylindrical phase, and (3) the 3D arrangement of spheres in body-centered-cubic (BCC) and hexagonal-closed-pack (HCP) morphologies in the spherical phase. The 3D data of the spherical morphologies was compared to coarse-grained simulations and assisted in validating the simulations' parameters. STEM tomography of SIS-treated BCP films enables the characterization of the exact structure used for pattern transfer and can lead to a better understating of the physics that is utilized in BCP lithography.

Chemical patterns for directed self-assembly (DSA) of lamellae-forming block copolymers (BCP) with density multiplication can be fabricated by patterning resist on a cross-linked polystyrene layer, etching to create guide stripes, and depositing end-grafted brushes in between the stripes as background. To date, two-tone chemical patterns have been targeted with the guide stripes preferentially wet by one block of the copolymer and the background chemistry weakly preferentially wet by the other block. In the course of fabricating chemical patterns in an all-track process using 300 mm wafers, it was discovered that the etching process followed by brush grafting could produce a three-tone pattern. We characterized the three regions of the chemical patterns with a combination of SEM, grazing-incidence small-angle X-ray scattering (GISAXS), and assessment of BCP-wetting behavior, and evaluated the DSA behavior on patterns over a range of guide stripe widths. In its best form, the three-tone pattern consists of guide stripes preferentially wet by one block of the copolymer, each flanked by two additional stripes that wet the other block of the copolymer, with a third chemistry as the background. Three-tone patterns guide three times as many BCP domains as two-tone patterns and thus have the potential to provide a larger driving force for the system to assemble into the desired architecture with fewer defects in shorter time and over a larger process window.