Hierarchically Ordered Hybrid and Quantum Materials from Additive Manufacturing and Block Copolymer Self-Assembly

Solution-based soft matter self-assembly promises unique materials properties from approaches including additive manufacturing/three-dimensional (3D) printing. This presentation will describe direct ink writing (DIW) derived, hierarchically porous transition metal nitrides and precursor oxides, structure-directed by Pluronics-family block copolymer self-assembly and heat treated in various environments. Resulting hierarchically ordered oxide and nitride materials show periodic lattices on three length scales in the form of atomic crystal lattices of oxides and nitrides, self-assembly derived periodic mesoscopic lattices in the form of hexagonal cylinder structures, and 3D printing derived periodic lattices in the form of woodpile and helical structures. By choosing appropriate thermal treatments, hierarchically ordered nitrides become superconducting. These superconducting structures show record nanoconfinement-induced upper critical magnetic field (B_c) enhancements correlated with block copolymer molar mass, mapping a macroscopic superconductor property onto a macromolecular design parameter, a true “first” for such materials. At the same time, they reach surface areas above 120 m²/g, the highest reported for compound superconductors to date. Moreover, embedded printing enables the first block copolymer self-assembly directed mesoporous non-self-supporting helical superconductors. Results suggest that additive manufacturing may open pathways to hierarchically ordered mesoporous quantum materials with not only a variety of macroscopic form factors but enhanced properties from intrinsic, self-assembly-derived mesostructures with substantial academic and technological promise.