Strong light localization inside the nanoscale gaps provides remarkable opportunities for creation of various medical and biosensing platforms stimulating an active search for inexpensive and easily scalable fabrication at a sub-100 nm resolution. In this paper, self-organized laser-induced periodic surface structures (LIPSSs) with the shortest ever reported periodicity of 70 ± 10 nm were directly imprinted on the crystalline Si wafer upon its direct femtosecond-laser ablation in isopropanol. Appearance of such a nanoscale morphology was explained by the formation of a periodic topography on the surface of photoexcited Si driven by interference phenomena as well as subsequent down-scaling of the imprinted grating period via Rayleigh−Taylor hydrodynamic instability. The produced deep subwavelength LIPSSs demonstrate strong anisotropic anti-reflection performance, ensuring efficient delivery of the incident far-field radiation to the electromagnetic "hot spots" localized in the Si nanogaps. This allows realization of various optical biosensing platforms operating via strong interactions of quantum emitters with nanoscale light fields. The demonstrated 80-fold enhancement of spontaneous emission from the attached nanolayer of organic dye molecules and in situ optical tracing of catalytic molecular transformations substantiate bare and metal-capped deep subwavelength Si LIPSSs as a promising inexpensive multifunctional biosensing platform.

Ultrashort laser pulses deliver electromagnetic energy to matter causing its localized heating that can be used for both material removal via ablation/evaporation and driving interface chemical reactions. Here, it is shown that both mentioned processes can be simultaneously combined within straightforward laser nanotexturing of Si wafer in a functionalizing solution to produce a practically relevant metal–semiconductor surface nano‐morphology. Such unique hybrid morphology represents deep‐subwavelength Si laser‐induced periodic surface structures (LIPSSs) with an extremely short period down to 70 nm and high‐aspect‐ratio nano‐trenches loaded with controllable amount of plasmonic nanoparticles formed via laser‐induced decomposition of the precursor noble‐metal salts. Moreover, heat localization driving reduction process is utilized to produce surface morphology locally decorated with dissimilar plasmon‐active nanoparticles. Light‐absorbing deep‐subwavelength Si LIPSSs loaded with controllable amount of noble‐metal nanoparticles represent an attractive architecture for plasmon‐related applications such as optical nanosensing where efficient coupling of the propagating optical waves to highly localized electromagnetic “hot spots” is a mandatory requirement. To support this statement, applicability of such hybrid morphology for fluorescence‐based detection of nanomolar concentrations of mercury cations in solution is demonstrated.

Here, we present the single-step laser-assisted fabrication of anti-reflective hierarchical surface textures on silicon locally functionalized with a photoluminescent (PL) molecular nanolayer. Using femtosecond-laser ablation of commercial crystalline Si wafers placed under a layer of a solution containing rhodamine 6G (R6G) a triethoxysilyl derivative, we fabricated ordered arrays of microconical protrusions with self-organized nanoscale surface morphology. At the same time, the laser-induced temperature increase facilitated surface activation and local binding of the R6G derivative to the as-fabricated nanotextured surface. The produced dual-scale surface textures showed remarkable broadband (visible to near-IR) light-absorbing properties with an averaged reflectivity of around 1%, and the capping molecular nanolayer demonstrated a strongly enhanced PL yield. By performing a pH sensing test using the produced nanotextured substrate, we confirmed the retention of sensory properties of the molecules attached to the surface and validated the potential applicability of the high-performing liquid-assisted laser processing as a key technology for the development of innovative multifunctional sensing devices in which the textured substrate (e.g., ultra-black semiconductor) plays a dual role as a support and PL signal amplifier.