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Abstract We demonstrate the use of tip-enhanced Raman spectroscopy (TERS) on polymeric microstructures fabricated by two-photon polymerization direct laser writing (TPP-DLW). Compared to the signal intensity obtained in confocal Raman microscopy, a linear enhancement of almost two times is measured when using TERS. Because the probing volume is much smaller in TERS than in confocal Raman microscopy, the effective signal enhancement is estimated to be ca. 10⁴. We obtain chemical maps of TPP microstructures using TERS with relatively short acquisition times and with high spatial resolution as defined by the metallic tip apex radius of curvature. We take advantage of this high resolution to study the homogeneity of the polymer network in TPP microstructures printed in an acrylic-based resin. We find that the polymer degree of conversion varies by about 30% within a distance of only 100 nm. The combination of high resolution topographical and chemical data delivered by TERS provides an effective analytical tool for studying TPP-DLW materials in a non-destructive way. 

Abstract Failure of materials and structures is inherently linked to localized mechanisms, from shear banding in metals, to crack propagation in ceramics and collapse of space‐trusses after buckling of individual struts. In lightweight structures, localized deformation causes catastrophic failure, limiting their application to small strain regimes. To ensure robustness under real‐world nonlinear loading scenarios, overdesigned linear‐elastic constructions are adopted. Here, the concept of delocalized deformation as a pathway to failure‐resistant structures and materials is introduced. Space‐tileable tensegrity metamaterials achieving delocalized deformation via the discontinuity of their compression members are presented. Unprecedented failure resistance is shown, with up to 25‐fold enhancement in deformability and orders of magnitude increased energy absorption capability without failure over same‐strength state‐of‐the‐art lattice architectures. This study provides important groundwork for design of superior engineering systems, from reusable impact protection systems to adaptive load‐bearing structures.