In the continuous downscaling of device features, the microelectronics industry is facing the intrinsic limits of conventional lithographic techniques. The development of new synthetic approaches for large-scale nanopatterned materials with enhanced performances is therefore required in the pursuit of the fabrication of next-generation devices. Self-assembled materials as block copolymers (BCPs) provide great control on the definition of nanopatterns, promising to be ideal candidates as templates for the selective incorporation of a variety of inorganic materials when combined with sequential infiltration synthesis (SIS). In this review, we report the latest advances in nanostructured inorganic materials synthesized by infiltration of self-assembled BCPs. We report a comprehensive description of the chemical and physical characterization techniques used for in situ studies of the process mechanism and ex situ measurements of the resulting properties of infiltrated polymers. Finally, emerging optical and electrical properties of such materials are discussed.

Besides causing financial losses and damage to the brand’s reputation, counterfeiting can threaten the health system and global security. In this context, physical unclonable functions (PUFs) have been proposed to overcome limitations of current anti-counterfeiting technologies. Here, we report on artificial fingerprints that can be directly engraved on a wide range of substrates through self-assembled block-copolymer templating as nanoscale PUFs for secure authentication and identification. Results show that morphological features can be exploited to encode fingerprint-like nanopatterns in binary code matrices representing a unique bit stream of information characterized by high uniqueness and entropy. A strategy based on computer vision concepts for authentication/identification in real-world scenarios is reported. Long-term reliable operation and robust authentication/identification against thermal treatment at cryogenic and high temperatures of the PUF have been demonstrated. These results pave the way for the realization of PUFs embracing the inherent stochasticity of self-assembled materials at the nanoscale.

Novel materials with defined composition and structures at the nanoscale are increasingly desired in several research fields spanning a wide range of applications. The development of new approaches of synthesis that provide such control is therefore required in order to relate the material properties to its functionalities. Self-assembling materials such as block copolymers (BCPs), in combination with liquid phase infiltration (LPI) processes, represent an ideal strategy for the synthesis of inorganic materials into even more complex and functional features. This review provides an overview of the mechanism involved in the LPI, outlining the role of the different polymer infiltration parameters on the resulting material properties. We report newly developed methodologies that extend the LPI to the realisation of multicomponent and 3D inorganic nanostructures. Finally, the recently reported implementation of LPI into different applications such as photonics, plasmonics and electronics are highlighted.

Metasurfaces have garnered increasing research interest in recent years due to their remarkable advantages, such as efficient miniaturization and novel functionalities compared to traditional optical elements such as lenses and filters. These advantages have facilitated their rapid commercial deployment. Recent advancements in nanofabrication have enabled the reduction of optical metasurface dimensions to the nanometer scale, expanding their capabilities to cover visible wavelengths. However, the pursuit of large-scale manufacturing of metasurfaces with customizable functions presents challenges in controlling the dimensions and composition of the constituent dielectric materials. To address these challenges, the combination of block copolymer (BCP) self-assembly and sequential infiltration synthesis (SIS), offers an alternative for fabrication of high-resolution dielectric nanostructures with tailored composition and optical functionalities. However, the absence of metrological techniques capable of providing precise and reliable characterization of the refractive index of dielectric nanostructures persists. This study introduces a hybrid metrology strategy that integrates complementary synchrotron-based traceable X-ray techniques to achieve comprehensive material characterization for the determination of the refractive index on the nanoscale. To establish correlations between material functionality and their underlying chemical, compositional and dimensional properties, TiO₂ nanostructures model systems were fabricated by SIS of BCPs. The results from synchrotron-based analyses were integrated into physical models, serving as a validation scheme for laboratory-scale measurements to determine effective refractive indices of the nanoscale dielectric materials.