The application of block copolymers (BCPs) for the fabrication of ultra-high-density addressable arrays, such as bit-patterned media (BPM), has been hampered by the poor intrinsic limit of thin film technology for long-range lateral ordering and orientation control over microdomains. [1][2][3][4][5][6] Chemically patterned substrates have been used to induce lateral ordering and to control the orientation of microdomains. [7][8][9][10] However, the resolution scalability, defined here as the ratio of the period patterned onto the surface and the natural period of the BCP, was limited to about a factor of 2. Additionally, when anisotropic BCP microdomains, such as cylinders or lamellae, are used, their orientation normal to the film surface (necessary for pattern transfer) requires the use of surfaces having balanced interfacial interactions with the blocks of the BCP and the use of BCPs with blocks having near-equal surface energies. Alternatively, the BCPs must be in nonequilibrium states that are susceptible to relaxation during thermal conditioning. In addition, to achieve small features, the microdomains of the BCP must be small, requiring the BCP to be in the strong segregation limit. This restricts the number of BCPs that are useful in achieving such small size scales; otherwise, additives must be used to enhance the microphase separation. It would be far more desirable to develop a process using BCPs with symmetric microdomains (spherical), so that it would be possible to take advantage of the differences in the interaction of the blocks with the substrate and in the surface energies of the blocks. This would make the process far more versatile and applicable to many different BCPs.Here, we used a BCP with spherical microdomains and a patterned substrate comprising a semidense hole-tone pattern in an ultrathin preferential wetting layer. As shown in Figure 1, the substrate was pretreated with a preferential wetting layer with a thickness of <10 nm consisting of a polymer brush with selective affinity for the major block of the copolymer. The surface energy of the minor component is lower than that of the major component, forcing a preferential segregation of the minor component to the free surface. The minor component also has a preferential affinity for the shallow patterned hole areas, which were formed by selectively removing the brush layer via an electron-beam lithography (EBL) process. Under these conditions, the equilibrium, and thus thermodynamically stable, structure of a film having a thickness 1.5 times the centerto-center distance of the spherical microdomains in the bulk (1.5 L 0 ), will consist of the lower surface energy component at its surface, pinned spherical microdomains of the minor component block covering the patterned features, and an array of spherical microdomains imbedded within the thin film. The pinned spherical microdomains may be spherelike, hemispherical, or even pancakelike, depending on the relative sizes of the patterned features and the natural BCP spherical domains. The...